Acridine derivatives and metal complexes thereof used for transparent recording medium or optical recording medium

ABSTRACT

An acridine derivative metal complex of formula 1 or formula 2 having a large absorption in the near-infrared range and a reduced absorption in the visible range, which acridine derivative metal complex is used in a transparent recording medium: ##STR1## where M is a metal atom, and X is a negative ion.

BACKGROUND

1. Field of the Invention

The present invention relates to an acridine derivative orphenanthridine derivative (hereinafter referred to as an indoanilinederivative) and metal complexes thereof useful in a transparentrecording medium from which a record having a visible ray absorption canbe obtained directly by using near infrared rays, and to a transparentrecording medium and optical recording medium, such as optical disksuseful in masking material for platemaking to be employed in theprinting step, and containing a new indoaniline metal complex.

2. Background of the Art

Thus far, the following recording mediums are known for obtainingrecording with visible-range absorption directly by heat. Aheat-sensitive recording medium used with a facsimile machine or thelike is made by applying a painting solution to an opaque support membersuch as paper which is obtained by dispersing and mixing a colorless orlight-colored electron donor substance (leuco dye) and an electronacceptor substance (developer) in an aqueous solution of a water-solublebinder and atomizing the mixed particles. Other transparent recordingmedia employing a nitrogen- or sulfur-containing onium compound as botha developer and thermal activator are prepared by dissolving a dye anddeveloper in an organic solvent and applying the obtained solution to atransparent support member, which are disclosed in Japanese PatentLaid-Open (ko-kai) Nos. 294088/1989 and 45087/1988. These are materialsfor recording an image by a direct heating method in which a recordingmedium is directly heated with a thermal head kept in contact with it.

On the other hand, members and methods for recording an image byirradiating near-infrared rays rather than by direct heating, aredisclosed in Japanese Patent Laid-Open (ko-kai) Nos. 94494 /1983,2880/1984 and 42994/1984. Japanese Patent Laid-Open (ko-kai) No.94494/1983 discloses an optical recording medium prepared by applying acoating liquid comprising not only a dye and a developer but also anear-infrared absorbing agent dispersed in a water-soluble binder to asupport member. Japanese Patent Laid-Open (ko-kai) Nos. 2880/1984,42994/1983 disclose optical recording media prepared by individuallylaminating a dye, a developer, and a near-infrared absorbing agent on asubstrate by vacuum evaporation. Also, Japanese Patent Laid-Open(ko-kai) No. 209594/1983 discloses a transparent recording mediumwherein so-called "background fogging" is prevented by the provision ofan isolating layer prepared by coating a solution of a near-infraredabsorbing agent in the interface between the coating layer prepared byapplying a solution of a leuco dye dissolved in an organic solvent to asubstrate and that of a developer solution provided thereabove.

Japanese Patent Laid-Open (ko-kai) No. 177950/1993 discloses atransparent recording medium wherein the relevant "background fogging"is completely prevented. In Japanese Patent Laid-Open (ko-kai) No.177950/1993, a complete prevention of "background fogging" isimplemented by the provision of a transparent recording layer formed bycoating a solution, comprising a developer expressed in the generalformula (5) mentioned above for protecting at least one of functionallydevelopable phenol-type hydroxide and a metal salt of organic acid or aleuco dye to develop a color in reaction with said developer dissolvedin an organic solvent, onto a transparent substrate. In Japanese PatentLaid-Open (ko-kai) No. 177950/1993, the transparent recording medium isemployed as an OHP (overhead projector) film, slide, copying draft, or aphoto mask for preparing the circuit pattern of a resin circuit board oran integrated circuit board. Near-infrared absorbing materials includeimmonium compounds such as IRG002 (trade name) and IRG022 (trade name)available from Nippon Kayaku K.K., dithiol nickel complexes, cyaninedyes such as 1,1,5,5-tetraxis (p-dimethylaminophenyl)-3-methoxy-1,4-pentadiene toluene, squalerium dyes, naphthoquinone dyes,phthalocyanine compounds, and naphthalocyanine compounds.

Furthermore, as an application of this transparent recording medium, amasking material for print platemaking can be mentioned. Withcomputerization of the printing process, various image forming methodsinterchangeable with conventional silver salt photography method areexamined in the platemaking step and also as proofs for colorproof-correction. In contrast to the silver salt photography methoddealing chiefly with analog images, the laser recording method, theelectronic photography method, the thermal transcription method, and thelike can also form an image by using a digital signal and can provide ahigh quality printing block material and color correction proof at highspeed. As a digital recording device, semiconductor lasers are mostoften employed from the standpoint of small size, durability, directconvertibility, low price and the like. As near-infrared sensitizersresponsive to near-infrared rays irradiated from a semiconductor laser,employed are near-infrared absorbing materials such as phthalocyaninecoloring substances described in Japanese Patent Publication (ko-koku)No. 64064/1991, heptamethine cyanine coloring substances described inJapanese Patent Publication (ko-koku) No. 28143/1990,naphthoindolenine-type cyanine coloring substances described in JapanesePatent Laid-Open (ko-kai) No. 273959/1994) and the like. Also, withrespect of image quality, silver salt photography still occupies thehighest position as the image forming method, but needs treating liquidsfor a developer, bleaching/fixing solution and the like. Since themaintenance and control of treating liquid quality is troublesome, thetreatment time is long, the disposal of development treating liquids isserious and so on, materials replacing silver salt photograph are beingcalled for.

Generally, near-infrared absorbing materials are often employed foroptical recording media such as optical disks. Optical disks givehigh-density recordings by irradiating near-infrared laser rays to arecording layer provided on a circular support member. A near-infraredabsorbing material contained in the recording layer efficiently convertsnear-infrared laser rays into heat and effects a thermodynamicdeformation such as decomposition, vaporization and dissolution.Playback of the recorded information is carried out by reading thedifference in reflectance between the generated portion of deformationby laser irradiation and the not-generated portion of deformation. Here,the performance required for near-infrared absorbing material is to havethe maximum wavelength of absorption near the wave length of laser raysto be used for recording, exhibit a high extinction coefficient at thiswave length, and have a high efficiency in converting light into heat.As examples of near-infrared absorbing materials employed fortransparent recording mediums, there can be mentionedphthalocyanine-type coloring substances described in Japanese PatentLaid-Open (ko-kai) No. 97033/1980, phenalen-type coloring substancesdescribed in Japanese Patent Laid-Open (ko-kai) No. 83344/1983,naphthoquinone-type coloring substance described in Japanese PatentLaid-Open (ko-kai) No. 224793/1983, and indoaniline metal complexesdescribed in Japanese Patent Laid-Open (ko-kai) Nos. 227569/1988,254772/1989, 568/1990, 667/1990. Furthermore, attempts were made toefficiently absorb laser rays by modifying the structure of theseindoaniline metal complexes in metal-contained compounds described inJapanese Patent Laid-Open (ko-kai) No. 73865/1990 and metal-containedpyridophenothiazone-type compounds described in Japanese PatentLaid-Open (ko-kai) No. 76884/1990, but neither a high recording densitynor a high contrast between the recorded portion and the unrecordedportion was obtained, so that no basic solution has been achieved.

In forming an image on a transparent recording medium by usingnear-infrared laser rays as a light source, it is required that anear-infrared absorbing material contained in the transparent recordingmedium efficiently absorb and convert into thermal energy the energy ofnear-infrared laser rays having a predetermined wavelength used for animage recording into thermal energy. Using a transparent recordingmedium as the masking material for print platemaking to be employed inthe printing step requires both a high recording density and a highcontrast between the portion recorded by laser rays and the unrecordedportion. Japanese Patent Laid-Open (ko-kai) No. 227569/1988 discloses asingle layer of indocyanine-type coloring substance provided on asubstrate, but this indocyanine-type coloring substance has anabsorption in the visible range and presents a problem in that a film ofthe single layer made by using this coloring substance develops a greencolor to form a recording medium lacking in contrast. Furthermore,cyanine-type coloring substances are generally subject to discolorationand fading by sunlight and have problems in light resistance and thelike.

In addition, in applications to optical recording media, a single layerof phthalocyanine-type coloring substance provided on a substrate,described in Japanese Patent Laid-Open (ko-kai) No. 97033/1980, hasproblems of low sensitivity, a high decomposition point and difficultvapor deposition, and further, problems of low solubility in organicsolvents and unavailability to coating by application. With thephenalene-type coloring substance described in Japanese Patent Laid-Open(ko-kai) No. 83344/1983 and the naphthoquinone-type coloring substancedescribed in Japanese Patent Laid-Open (ko-kai) No. 224793/1983, becausethe efficiency of converting light into heat is low despite the easinessof vapor deposition, the thermal deformation in the portion irradiatedby laser rays is insufficient and a contrast in reflectance between therecorded portion and the unrecorded portion decreases in the playback ofinformation and the playback of information becomes difficult. Becauseof being generally inferior in stability for laser rays employed duringplayback, organic coloring substances have another problem that theconversion efficiency declines when additional-recording by laser rays,thereby disabling information to be recorded.

With due consideration for the present circumstances, it is one objectof the present invention to provide a transparent recording medium, highin recording density, good in contrast and excellent in longevity suchas light resistance, by using new indoaniline metal complexes and theircompounds, high in near-infrared absorption, highly efficient inconverting light into heat, low in visible absorption, and further,highly soluble in an organic solvent, capable of coating by application,and excellent in longevity such as light resistance.

SUMMARY OF THE INVENTION

As a result of intensive studies for solving the problems mentionedabove, the present authors find how the problems mentioned above of aconventional transparent recording medium can be solved at once by usingnew indoaniline metal complexes according to the present invention asnear-infrared absorbing materials in a transparent recording medium madeby applying a solution, comprising (a) a developer and (b) metal saltsof organic acids to develop a color in reaction with said developer, ora leuco dye, dissolved in an organic solvent, to a transparent supportmember, thereby leading to the perfection of the present invention.

As compared with the metal-containing indoaniline-type complex compoundsdescribed in Japanese Patent Laid-Open (ko-kai) No. 227569/1988, newindoaniline metal complexes according to the present invention, with anextended maximum wavelength of absorption, has a high absorption in thenear-infrared range. And as compared with said publicly knownmetal-containing indoaniline-type complex compounds, the molarextinction coefficient also increases extremely and the efficiency ofconverting near-infrared laser rays into heat greatly rises. Even byusing a small-output semiconductor near-infrared laser ray, an imagehaving a sufficiently high recording density can be obtained on atransparent recording medium.

In a new indoaniline metal complex according to the present invention,since the conjugate system spreads out as compared with said publiclyknown metal-containing indoaniline-type complex compounds, theabsorption spectrum is greatly shifted from the visible range to thenear-infrared range. Because the absorption in the visible rangedecreases because of this red-shifting, the new indoaniline metalcomplex is slightly colored and the transparent recording medium made byusing this as a near-infrared absorbing material for optical recordingalso has a low absorption in the visible range and slightly develops acolor. The extinction coefficient greatly increases and the efficiencyof converting near-infrared laser rays into heat greatly rises as well.Consequently, the recording density in recording by near-infrared laserrays is very high and the contrast in the obtained image is excellent. Anew indoaniline metal complex exhibits a high solubility in organicsolvents and is capable of coating by application. Generally, coloringsubstances having a metal complex structure are stable under ultravioletlight contained in sunlight or the like and include coloring substancesfunctioning as a singlet oxygen quencher. Because of no discolorationand no change in the molar extinction coefficient or in the efficiencyof converting near-infrared laser rays into heat even on a long exposureunder sunlight, a new indoaniline metal complex according to the presentinvention is a coloring substance which is excellent in light resistanceand the transparent recording medium made by using this complex is alsoexcellent in light resistance.

That is, the present invention refers to a new indoaniline metalcomplex, suitable for a near-infrared absorbing material for opticalrecording applicable to transparent recording media on which a recordwith an absorption in the visible range can be obtained directly bynear-infrared laser rays, represented by the following general formula(1): ##STR2## (in the formula, M denotes a metal atom, R¹ and R² denotea hydrogen atom, alkyl group, or aryl group, R³ denotes a hydrogen atomor electron donating groups, and R⁴, R⁵ and R⁶ denote a hydrogen atom orelectron withdrawing groups, whereas i, j and k denote an integer of 1,2 or 3, 1 and n denote an integer of 1-4, m denotes 1 or 2, and Xdenotes a negative ion) and by the following general formula (2):##STR3## (in the formula, M denotes a metal atom, R¹ and R² denote ahydrogen atom, alkyl group, or aryl group, R³ denotes a hydrogen atom orelectron donating groups, and R⁴, R⁷ and R⁸ denote a hydrogen atom orelectron withdrawing groups, whereas i, j and k denote an integer of 1,2 or 3, 1 and o denote an integer of 1-4, m denotes 1 or 2, and Xdenotes a negative ion).

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a spectral chart of ¹ H-NMR forN-(2-chlorobenzylidene)-2'-hydroxyaniline (12) obtained in PreparedExample 1-1-1.

FIG. 2 is a spectral chart of ¹³ C-NMR forN-(2-chlorobenzylidene)-2'-hydroxyaniline (12) obtained in PreparedExample 1-1-1.

FIG. 3 is a spectral chart of ¹ H-NMR for 4-hyroxyphenanthridine (13)obtained in Prepared Example 1-1-2.

FIG. 4 is a spectral chart of ¹³ C-NMR for 4-hyroxyphenanthridine (13)obtained in Prepared Example 1-1-2.

FIG. 5 is a spectral chart of ¹ H-NMR for indoaniline (22) obtained inPrepared Example 1-1-3.

FIG. 6 is a chart of IR spectrum for the indoaniline metal complex (24)obtained in Prepared Example 1-1-4.

FIG. 7 is a chart of visible to near-infrared absorption spectrum forthe indoaniline metal complex (24) obtained in Prepared Example 1-1-4and the indoaniline metal complex (27) obtained in Comparative Example1-1, where the ordinate represents an absorbance and the abscissarepresents a wavelength (nm).

FIG. 8 is a spectral chart of ¹ H-NMR for the indoaniline metal complex(25) obtained in Preparing Example 2-1-6.

FIG. 9 is a spectral chart of ¹³ C-NMR for the indoaniline metal complex(25) obtained in Preparing Example 2-1-6.

FIG. 10 is a chart of IR spectrum for the indoaniline metal complex (25)obtained in Preparing Example 2-1-6.

FIG. 11 is a chart of IR spectrum for the indoaniline metal complex (26)obtained in Preparing Example 2-1-7.

FIG. 12 is a chart of visible to near-infrared absorption spectrum forthe indoaniline metal complex (26) obtained in Preparing Example 2-1-7and the indoaniline metal complex (27) obtained in Comparative Example1-1, where the ordinate represents an absorbance and the abscissarepresents a wavelength (nm).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Hereinafter, the present invention will be described in detail byreferring to specific examples. As a metal atom denoted by M in theabove-mentioned general formulae (1) or (2), Ni, Cu, Co, Zn, Fe, Pd, Ptor the like is mentioned. Among them, Ni, Cu, Co, Fe or the like ispreferable metal atom.

Examples can be given of alkyl groups denoted by R¹ and R² as follows:methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,tert-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, lauryl, myristyl,palmityl, stearyl, 2-propenyl, 2-methyl-2-propenyl, 2-chloro-2-propenyl,2-hydroxyethyl, 2-cyanoethyl, 2-aminoethyl, 2-chloroethyl, 2-bromoethyl,2-iodoethyl, 2-fluoroethyl, trifluoromethyl, 2,2,2- trifluoroethyl,2-methoxyethyl, 2-ethoxyethyl, methoxyethoxyethyl, 2-allyloxyethyl,benzyl, phenethyl, benzyloxymethyl, 2-benzyloxyethyl,methylcarbonyloxyethyl, benzylcarbonyloxymethyl, 2-phenoxyethyl,2-acetoxyethyl, 2-carboxyethyl, ethoxycarbonylmethyl,methoxycarbonylethyl, 3-mesylpropyl, 2-furylmethyl, 2-oxolanylmethyl,cyclopentyl, cyclohexyl and 2-methylcyclohexyl, whereas examples of arylgroups are given as follows: phenyl, o-tolyl, m-tolyl, p-tolyl,o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-bromophenyl,m-bromophenyl, p-bromophenyl, o-methoxyphenyl, m-methoxyphenyl,p-methoxyphenyl, p-ethoxyphenyl and p-n-butoxyphenyl. In addition, R'sand R² s may directly form rings, whose examples are ring structuressuch as pyrolidine, imidazolidine, piperidine, piperazine, morpholineand indoline. Examples can be given of electron donating groups denotedby R³ as follows: alkyl groups, aralkyl groups, alkoxy groups, aryloxygroups, alkylthio groups, arylthio groups, alkyl-substituted aminogroups, acylamino groups, sulfonylamino groups, and ureido groups. To bespecific, alkyl groups include methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl,2-ethylhexyl, lauryl, myristyl, parmityl, stearyl, 2-hydroxyethyl,2-cyanoethyl, 2-aminoethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl,2-fluoroethyl, 2,2,2-trifluoroethyl, 2-methoxyethyl, methoxyethoxyethyl,2-allyloxyethyl, benzyl, phenetyl, benzyloxymethyl, 2-benzyloxyethyl,methylcarbonyloxyethyl, benzylcarbonyloxymethyl, 2-phenoxyethyl,2-acetoxyethyl, 2-carboxyethyl, ethoxycarbonylmethyl,methoxycarbonylethyl, 3-mesylpropyl, 2-furylmethyl, 2-oxolanylmethyl,cyclopentyl, cyclohexyl and 2-methylcyclohexyl; aralkyl groups includebenzyl, phenethyl, benzhydrol and trityl; alkoxy groups include methoxy,ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, andtert-butoxy; aryloxy groups include phenoxy, o-tolyloxy, m-tolyloxy,p-tolyloxy, o-chlorophenoxy, m-chlorophenoxy, p-chlorophenoxy,o-bromophenoxy, m-bromophenoxy, p-bromophenoxy, o-methoxyphenoxy,m-methoxyphenoxy, p-methoxyphenoxy, p-ethoxyphenoxy and p-butoxyphenoxy;alkylthio groups include methylthio, ethylthio, n-propylthio,iso-propylthio, n-butylthio, iso-butylthio, sec-butylthio,tert-butylthio and benzylthio; arylthio groups include phenylthio,o-tolylthio, m-tolylthio, p-tolylthio, o-chlorophenylthio,m-chlorophenylthio, p-chlorophenylthio, o-bromophenylthio,m-bromophenylthio, p-bromophenylthio, o-methoxyphenylthio,m-methoxyphenylthio, p-methoxyphenylthio, p-ethoxyphenylthio andp-butoxyphenylthio; and alkyl-substituted amino groups includedimethylamino, diethylamino, di-n-propylamino, di-iso-propylamino,di-n-butylamino, di-iso-butylamino, di-sec-butylamino,di-tert-butylamino, N-methyl-N-ethylamino, N-ethyl-N-iso-propylamino andN-ethyl-N-n-butylamino; acylamino groups include formylamino,acetylamino, propionylamino, butyrylamino, iso-butyrylamino,valerylamino, iso-valerylamino, pivaloylamino, lauroylamino,myristoylamino, palmitoylamino, stearoylamino, benzoylamino,1-naphthoylamino and 2-naphthoylamino; sulfonylamino groups includemesylamino, ethanesulfonylamino and tosylamino; ureido groups includeureido, N-methylureido, N-n-propylureido, N-N-diethylureido,N-acetyl-N-phenylureodo, thioureido, N-methylthioureido,N-N-diethylthioureido and N-acetyl-N-phenylthioureodo.

Examples can be given of electron withdrawing groups denoted by R⁴, R⁵,R⁶, R⁷ and R⁸ as follows: halogen atoms, trifluoromethyl, aryl groups,carbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups,carbamoyl groups, sulfonyl groups, sulfamoyl groups, nitro, and cyano.To be specific, halogen atoms include chlorine, bromine, iodine andfluorine; aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl,o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-bromophenyl,m-bromophenyl, p-bromophenyl, o-hydroxyphenyl, o-methoxyphenyl,m-methoxyphenyl, p-methoxyphenyl, p-ethoxyphenyl and p-butoxyphenyl;carbonyl groups include formyl, acetyl, propionyl, butyryl, iso-butyryl,valeryl, iso-valeryl, pivaloyl, lauroyl, myristoyl, palmitoyl, stearoyl,benzoyl, 1-naphthoyl and 2-naphthoyl; alkoxycarbonyl groups includemethoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso-propoxycarbonyl,n-butoxycarbonyl, iso-butoxycarbonyl, sec-butoxycarbonyl,tert-butoxycarbonyl, lauryloxycarbonyl, myristyloxycarbonyl,palmityloxycarbonyl and stearyloxycarbonyl; aryloxycarbonyl groupsinclude phenoxycarbonyl, o-tolyloxycarbonyl, m-totolyloxycarbonyl,p-tolyloxycarbonyl, o-chlorophenoxycarbonyl, m-chlorophenoxycarbonyl,p-chlorophenoxycarbonyl, o-bromophenoxycarbonyl, m-bromophenoxycarbonyl,p-bromophenoxycarbonyl, o-methoxyphenoxycarbonyl,m-methoxyphenoxycarbonyl, p-methoxyphenoxycarbonyl,p-ethoxyphenoxycarbonyl, p-butoxyphenoxycarbonyl,hydroxyiminomethylcarbonyl, bromoacetyl, hydroxycarbonyl,methoxycarbonyl, n-hexylcarbonyl, aminothiocarbonyl, andhydroxycarbonylmethyl; carbamoyl groups include N-phenylcarbamoyl,N-4-bromophenylcarbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl,N-2-hydroxyethylcarbamoyl, N-2-methoxyethylcarbamoyl,N-ethoxymethylcarbamoyl, N-oxolanyl-methyl-carbamoyl, N-allylcarbamoyl,N-2-thienylcarbamoyl, N-3-(2-methoxycarbonyl)thienylcarbamoyl,N-2-(4-nitro)thienylcarbamoyl, N-2-thiazolylcarbamoyl,N-(4-methylsulfonyl)phenylcarbamoyl, N-(4-cyano) phenylcarbamoyl,N-2-benzomidazolylcarbamoyl, N-2-benzoxazolylcarbamoyl,N-2-benzothiazolylcarbamoyl, N-2-pyridylcarbamoyl, N-4-pyridylcarbamoyl,N-4-pyrimidylcarbamoyl, N-2-quinolylcarbamoyl, N-4-quinolylcarbamoyl andN-3H-indo-2-lylcarbamoyl; sulfonyl groups include mesyl, ethanesulfonyland tosyl; and sulfamoyl groups include N-phenylsulfamoyl,N-4-bromophenylsulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl,N-2-hydroxyethylsulfamoyl, N-2-methoxyethylsulfamoyl,N-ethoxymethylsulfamoyl, N-oxolanylmetylsulfamoyl, N-allylsulfamoyl,N-2-thienylsulfamoyl, N-2-(4-nitro)thienylsulfamoyl,N-2-thiazolylsulfamoyl, N-(4-methylsulfonyl)phenylsulfamoyl,N-(4-cyano)phenylsulfamoyl, N-phenyl(4-cyano)sulfamoyl,N-2-benzoimidazolylsulfamoyl, N-2-benzoxazolylsulfamoyl,N-2-benzothiazolylsulfamoyl, N-2-pyridylsulfamoyl, N-4-pyridylsulfamoyl,N-4-pyrimidylsulfamoyl, N-2-quinolylsulfamoyl, N-4-quinolylsulfamoyl andN-3H-indo-2-lylsulfamoyl.

Negative ions denoted by X include F⁻, Cl⁻, Br⁻, I⁻, ClO₄ ⁻, SCN⁻, BF₄⁻, PF₆ ⁻, SbF₆ ⁻, TiF₆ ²⁻, ZrF₆ ²⁻, SiF₆ ²⁻, OH⁻, TsO⁻, HCOO⁻, CH₃ COO⁻,NO₃ ⁻, H₂ PO₄ ⁻, BPh₄ ⁻ and CN⁻, but preferably are Cl⁻, Br⁻, I⁻, ClO₄⁻, BF₄ ⁻, PF₆ ⁻ and SbF₆ ⁻.

Hereinafter, specific examples of new indoaniline metal complexesrepresented by the following general formulae (1) and (2) will bementioned, but the present invention is not limited to these examples.In the tables that follow, l, m, n, and o are indicated as 0 (zero)where the appropriate R group is a hydrogen atom, i.e., l, m, n, and oare technically 1 (one). ##STR4##

                                      TABLE 1                                     __________________________________________________________________________    No.                                                                              R.sup.1  R.sup.2    R.sup.3                                                                            R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         M X  i j k l m n                            __________________________________________________________________________    1-1                                                                              ethyl    ethyl      8-methyl                                                                           H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                            1-2                                                                              ethyl    ethyl      H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-3                                                                              methyl   methyl     H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-4                                                                              n-propyl n-propyl   H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-5                                                                              i-propyl i-propyl   H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-6                                                                              n-butyl  n-butyl    H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-7                                                                              s-butyl  H          H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-8                                                                              n-pentyl n-pentyl   H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-9                                                                              n-hexyl  n-hexyl    H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-10                                                                             2-ethylhexyl                                                                           2-ethylhexyl                                                                             H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-11                                                                             cetyl    cetyl      H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-12                                                                             ethyl    2-cyanoethyl                                                                             H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-13                                                                             ethyl    2-chloroethyl                                                                            H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-14                                                                             2-ethoexyethyl                                                                         2-ethoxyethyl                                                                            H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-15                                                                             methoxyethoxyethyl                                                                     methoxyethoxyethyl                                                                       H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-16                                                                             benzyl   benzyl     H    H Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-17                                                                             ethyl    benzyloxyethyl                                                                           H    H Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-18                                                                             ethyl    methylcarbonyloxyethyl                                                                   H    H Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-19                                                                             ethyl    2-phenoxyethyl                                                                           H    H Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-20                                                                             ethyl    2-acetoxyethyl                                                                           H    H Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-21                                                                             2-carboxyethyl                                                                         2-carboxyethyl                                                                           H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    No.                                                                              R.sup.1   R.sup.2   R.sup.3                                                                              R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         M X  i j k l m n                          __________________________________________________________________________    1-22                                                                             ethoxycarbonylmethyl                                                                    ethoxycarbonylmethyl                                                                    H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-23                                                                             3-mesylpropyl                                                                           3-mesylpropyl                                                                           H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-24                                                                             ethyl     2-oxolanylmethyl                                                                        H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-25                                                                             H         phenyl    H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-26                                                                             H         p-tolyl   H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-27                                                                             H         p-chlorophenyl                                                                          H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-28                                                                             H         p-methoxyphenyl                                                                         H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-29                                                                             H         p-n-butoxyphenyl                                                                        H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-30                                                                             2-propenyl                                                                              2-propenyl                                                                              H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-31                                                                             ethyl     2-methyl-2-propenyl                                                                     H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-32                                                                             ethyl     2-chloro-2-propenyl                                                                     H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-33                                                                             ethyl     cyclohexyl                                                                              H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-34                                                                             piperidinyl         H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-35                                                                             morpholinyl         H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          1-38                                                                             ethyl     ethyl     8-ethyl                                                                              H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                          1-39                                                                             ethyl     ethyl     8-cyclohexyl                                                                         H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                          1-40                                                                             ethyl     ethyl     8-phenyl                                                                             H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                          1-41                                                                             ethyl     ethyl     8-(2-propenyl)                                                                       H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                          1-42                                                                             ethyl     ethyl     8-benzyl                                                                             H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                          __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    No.                                                                              R.sup.1   R.sup.2   R.sup.3   R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         M X  i j k l m n                       __________________________________________________________________________    1-43                                                                             ethyl     ethyl     8-methoxy H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       1-44                                                                             2-phenoxyethyl                                                                          2-phenoxyethyl                                                                          8,10-diethoxy                                                                           H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 2 0 0                       1-45                                                                             2-ethoyxethyl                                                                           2-ethoxyethylhyl                                                                        8-methoxy-10-methyl                                                                     H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 2 0 0                       1-49                                                                             n-butyl   n-butyl   8-diethylamino                                                                          H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       1-50                                                                             n-butyl   n-butyl   8-diisopropylamino                                                                      H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       1-51                                                                             n-butyl   n-butyl   8-tosylamino                                                                            H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       1-52                                                                             ethyl     ethyl     8-mesylamino                                                                            H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       1-53                                                                             n-butyl   n-butyl   8-laurolyamino                                                                          H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       1-54                                                                             ethyl     ethyl     8-palmitoylamino                                                                        H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       1-55                                                                             ethyl     ethyl     8-stearoylamino                                                                         H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       1-56                                                                             ethyl     ethyl     8-(1-naphthoylamino)                                                                    H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       1-57                                                                             2-ethylhexyl                                                                            2-ethylhexyl                                                                            H         H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       1-58                                                                             2-ethylhexyl                                                                            2-ethylhexyl                                                                            H         H H H Fe                                                                              ClO.sub.4                                                                        3 2 3 1 0 0                       1-59                                                                             ethyl     ethyl     8-n-butylthio                                                                           H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       1-60                                                                             n-butyl   n-butyl   8-phenylethio                                                                           H H H Cu                                                                              Cl 2 2 2 1 0 0                       1-61                                                                             ethyl     ethyl     8-p-chlorophenylthio                                                                    H H H Cu                                                                              Br 2 2 2 1 0 0                       1-62                                                                             n-butyl   n-butyl   8-benzylthio                                                                            H H H Cu                                                                              I  2 2 2 1 0 0                       1-63                                                                             ethyl     ethyl     8-ureido  H H H Cu                                                                              BF.sub.4                                                                         2 2 2 1 0 0                       __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    No.                                                                              R.sup.1                                                                           R.sup.2                                                                           R.sup.3  R.sup.4       R.sup.5                                                                         R.sup.6                                                                         M X  i j k l m n                        __________________________________________________________________________    1-64                                                                             n-butyl                                                                           n-butyl                                                                           8-N-n-propylureido                                                                     H             H H Cu                                                                              PF.sub.6                                                                         2 2 2 1 0 0                        1-65                                                                             ethyl                                                                             ethyl                                                                             8-N,N-diethylureido                                                                    H             H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        1-66                                                                             ethyl                                                                             ethyl                                                                             8-thioureido                                                                           H             H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        1-67                                                                             ethyl                                                                             ethyl                                                                             8-N-acetyl-                                                                            H             H H Cu                                                                              SbF.sub.6                                                                        2 2 2 1 1 0                                   N-phenylthioureido                                                 1-68                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-acetyl      H H Cu                                                                              ClO.sub.4                                                                        2 3 2 1 1 0                        1-69                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-isovaleryl  H H Cu                                                                              ClO.sub.4                                                                        2 3 2 1 1 0                        1-70                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-stearoyl    H H Cu                                                                              ClO.sub.4                                                                        2 3 2 1 1 0                        1-71                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-benzoyl     H H Cu                                                                              ClO.sub.4                                                                        2 3 2 1 1 0                        1-72                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(1-naphthoyl)                                                                             H H Cu                                                                              ClO.sub.4                                                                        2 3 2 1 1 0                        1-73                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-carboxy     H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        1-74                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-N-phenylcarbamoyl                                                                         H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        1-75                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-N-methylcarbamoyl                                                                         H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        1-76                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-N-          H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                            ethoxymnethylcarbamoyl                                    1-77                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-2-       H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                            oxolanylmethylcarbamoyl)                                  1-78                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-N-allylcarbamoyl                                                                          H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        1-79                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-3-(2-methoxycarbonyl)                                                                  H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                            thienylcarbamoyl)                                         1-80                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-N-2-thiazaolylacarbamoyl                                                                  H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        1-81                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-2-       H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                            benzoimidazolylcarbamoyl)                                 1-82                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-2-       H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                            benzoxazolylcarbamoyl)                                    1-83                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-2-       H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                            benzothiazolylcarbamoyl)                                  1-84                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-2-pyridylcarbamoyl)                                                                    H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        __________________________________________________________________________

                                      TABLE 5                                     __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4      R.sup.5                                                                         R.sup.6                                                                         M X  i j k l m n                               __________________________________________________________________________    1-85                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-pyrimidylcarbamoyl)                                                                 H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-86                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-quinolylcarbamoyl)                                                                  H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-87                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-3H-indo-2-lylcarbamoyl)                                                               H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-88                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-sulfo      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-89                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-phenylsulfamoyl                                                                        H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-90                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-methylsulfamoyl                                                                        H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-91                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-ethoxymethylsulfamoyl)                                                                 H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-92                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                             oxolanylmethylsulfamoyl)                                        1-93                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-allylsulfamoyl                                                                         H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-94                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-thienylsulfamoyl)                                                                   H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-95                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-thiazolylsulfamoyl)                                                                 H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-96                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                             benzoimidazolylsulfamoyl)                                       1-97                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                             benzoxazolylsulfamoyl)                                          1-98                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                             benzothiazolylsulfamoyl)                                        1-99                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-pyridylsulfamoyl)                                                                   H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-100                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-pyrimidylsulfamoyl)                                                                 H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-101                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-quinolylsulfamoyl)                                                                  H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-102                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-3H-indo-2-lylsulfamoyl)                                                               H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-103                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-methoxycarbonyl                                                                          H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-104                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-ethoxycarbonyl                                                                           H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-105                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-n-butoxycarbonyl                                                                         H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4      R.sup.5                                                                         R.sup.6                                                                         M X  i j k l m n                               __________________________________________________________________________    1-106                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-lauryloxycarbonyl                                                                        H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-107                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-stearyloxycarbonyl                                                                       H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-108                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-phenoxycarbonyl                                                                          H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-109                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-p-tolyloxycarbonyl                                                                       H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-110                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-p-chlorophenoxycarbonyl                                                                  H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-111                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-p-methoxyphenocarbonyl                                                                   H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-112                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-nitro      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-113                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-nitro      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-117                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-chloro     H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-118                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-chloro     H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-119                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-bromo      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-120                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-fluro      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               1-121                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H            Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                               __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4                                                                         R.sup.5                                                                         R.sup.6  M X  i j k l m n                                   __________________________________________________________________________    1-127                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 3-chloro Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-128                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-chloro Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-129                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-chloro Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-130                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-chloro Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-131                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-fluro  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-133                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-phenyl Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-139                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-methoxyethoxy                                                                        Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 2                                   1-140                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-methoxycarbonyl                                                                      Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-141                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-ethoxycarbonyl                                                                       Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-142                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-cyano  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 i                                   1-143                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-trifluoremethyl                                                                      Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-144                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-trifluoremethyl                                                                      Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-146                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 3-nitro  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-147                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-nitro  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4                                                                         R.sup.5                                                                         R.sup.6  M X  i j k l m n                                   __________________________________________________________________________    1-148                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-carboxyl                                                                             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-149                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-carboxyl                                                                             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-150                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-phenoxycarbonyl                                                                      Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-151                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-p-     Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     tolyloxycarbonyl                                            1-152                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-o-     Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     bromophenoxy-                                                                 carbonyl                                                    1-153                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-acety  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-154                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-propionyl                                                                            Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-155                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-isovaleryl                                                                           Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-156                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-stearoyl                                                                             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-157                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-benzoyl                                                                              Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   1-158                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-     Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     phenylcarbamoyl                                             1-159                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-N-     Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     methylcarbamoyl                                             1-160                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-N-     Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     allylcarbamoyl                                              1-161                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     thienylcarbamoyl)                                           1-162                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-     Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     benzothizoly-                                                                 carbamoyl                                                   1-163                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     pyridylcarbamoyl)                                           1-164                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-3H-indo-                                                                          Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     2-lylcarbamoyl)                                             1-165                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-     Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     phenylsulfamoyl                                             1-166                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H Me                                                                              4-N-     Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     methylsulfamoyl                                             1-167                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-(N-2-  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     oxolanyl-                                                                     methysulfamoyl)                                             1-168                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                     thiazolylsulfamoyl)                                         __________________________________________________________________________

                                      TABLE 9                                     __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4                                                                         R.sup.5 R.sup.6       M X  i j k l m n                        __________________________________________________________________________    1-169                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H       4-N-benzoimidazolylsulfamoyl                                                                Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                        1-170                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H       6-(N-2-pyrimidylsulfamoyl)                                                                  Fe                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                        1-171                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H F       H             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        1-172                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H Cl      H             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        1-173                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H Br      H             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        1-176                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H cyano   H             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        1-179                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H o-hydroxyphenyl                                                                       H             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        1-180                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H 3-pyridinyl                                                                           H             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        1-183                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H ethoxy  H             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        1-188                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H formyl  H             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        1-189                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H acetyl  H             Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        __________________________________________________________________________

                                      TABLE 10                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                             R.sup.2                                                                             R.sup.3                                                                         R.sup.4                                                                         R.sup.5      R.sup.6                                                                         M X  i j k l m n                            __________________________________________________________________________    1-190                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H hydroxyiminomethylcarbonyl                                                                 H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-191                                                                            2-ethylhexyl                                                                        2-ethylhexy                                                                         H H bromoyl      H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-192                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H hydroxycarbonyl                                                                            H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-193                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H methoxycarbonyl                                                                            H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-194                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H n-hexylcarbonyl                                                                            H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            1-195                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H aminothiocarbonyl                                                                          H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            __________________________________________________________________________     ##STR5##                                                                  

                                      TABLE 11                                    __________________________________________________________________________    No.                                                                              R.sup.1  R.sup.2    R.sup.3                                                                            R.sup.4                                                                         R.sup.7                                                                         R.sup.8                                                                         M X  i j k l m o                            __________________________________________________________________________    2-1                                                                              ethyl    ethyl      8-methyl                                                                           H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                            2-2                                                                              ethyl    ethyl      H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-3                                                                              methyl   methyl     H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-4                                                                              n-propyl n-propyl   H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-5                                                                              i-propyl i-propyl   H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-6                                                                              n-butyl  n-butyl    H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-7                                                                              s-butyl  H          H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-8                                                                              n-pentyl n-pentyl   H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-9                                                                              n-heyxl  n-hexyl    H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-10                                                                             2-ethylhexyl                                                                           2-ethylhexyl                                                                             H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-11                                                                             cetyl    cetyl      H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-12                                                                             ethyl    2-cyanoethyl                                                                             H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-13                                                                             ethyl    2-chloroethyl                                                                            H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-14                                                                             2-ethoxyethyl                                                                          2-ethoxyethyl                                                                            H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-15                                                                             methoxyethoxyethyl                                                                     methoxyethoxyethyl                                                                       H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-16                                                                             benzyl   benzyl     H    H Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-17                                                                             ethyl    benzyloxyethyl                                                                           H    H Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-18                                                                             ethyl    methylcarbonyloxyethyl                                                                   H    H Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-19                                                                             ethyl    2-phenoxyethyl                                                                           H    H Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-20                                                                             ethyl    2-acetoxyethyl                                                                           H    H Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-21                                                                             2-carboxyethyl                                                                         2-carboxyethyl                                                                           H    H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            __________________________________________________________________________

                                      TABLE 12                                    __________________________________________________________________________    No.                                                                              R.sup.1   R.sup.2   R.sup.3                                                                              R.sup.4                                                                         R.sup.7                                                                         R.sup.8                                                                         M X  i j k l m o                          __________________________________________________________________________    2-22                                                                             ethoxycarbonylmethyl                                                                    ethoxycarbonylmethyl                                                                    H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                          2-23                                                                             3-mesylpropyl                                                                           3-mesylpropyl                                                                           H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-24                                                                             ethyl     2-oxolanylmethyl                                                                        H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-25                                                                             H         phenyl    H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-26                                                                             H         p-tolyl   H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-27                                                                             H         p-chlorophenyl                                                                          H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-28                                                                             H         p-methoxyphenyl                                                                         H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-29                                                                             H         p-n-butoxyphenyl                                                                        H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-30                                                                             2-propenyl                                                                              2-propenyl                                                                              H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-31                                                                             ethyl     2-methyl-2-propenyl                                                                     H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-32                                                                             ethyl     2-chloro-2-propenyl                                                                     H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-33                                                                             ethyl     cyclohexyl                                                                              H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-34                                                                             piperidinyl         H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-35                                                                             morpholinyl         H      H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                          2-39                                                                             ethyl     ethyl     8-cyclohexyl                                                                         H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                          2-41                                                                             ethyl     ethyl     8-(2-propenyl)                                                                       H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                          2-42                                                                             ethyl     ethyl     8-benzyl                                                                             H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                          __________________________________________________________________________

                                      TABLE 13                                    __________________________________________________________________________    No.                                                                              R.sup.1   R.sup.2   R.sup.3   R.sup.4                                                                         R.sup.7                                                                         R.sup.8                                                                         M X  i j k l m o                       __________________________________________________________________________    2-43                                                                             ethyl     ethyl     8-methoxy H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-44                                                                             2-phenoxyethyl                                                                          2-phenoxyethyl                                                                          8,10-diethoxy                                                                           H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 2 0 0                       2-45                                                                             2-ethoxyethyl                                                                           2-ethoxyethyl                                                                           8-methoxy-10-methyl                                                                     H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 2 0 0                       2-49                                                                             n-butyl   n-butyl   8-diethylamino                                                                          H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-50                                                                             n-butyl   n-butyl   8-diisopropylamino                                                                      H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-51                                                                             n-butyl   n-butyl   8-tosylamino                                                                            H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-52                                                                             ethyl     ethyl     8-mesylamino                                                                            H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-53                                                                             n-butyl   n-butyl   8-laurolyamino                                                                          H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-54                                                                             ethyl     ethyl     8-palmitoylamino                                                                        H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-55                                                                             ethyl     ethyl     8-stearoylamino                                                                         H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-56                                                                             ethyl     ethyl     8-(1-naphthoyl)amino                                                                    H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-57                                                                             2-ethylhexyl                                                                            2-ethylhexyl                                                                            H         H H H Ni                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                       2-58                                                                             2-ethylhexyl                                                                            2-ethylhexyl                                                                            H         H H H Fe                                                                              ClO.sub.4                                                                        3 2 3 0 0 0                       2-59                                                                             ethyl     ethyl     8-n-butylthio                                                                           H H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-60                                                                             n-butyl   n-butyl   8-phenylthio                                                                            H H H Cu                                                                              Cl 2 2 2 1 0 0                       2-61                                                                             ethyl     ethyl     8-p-chlorophenylthio                                                                    H H H Cu                                                                              Br 2 2 2 1 0 0                       2-62                                                                             n-butyl   n-butyl   8-benzylthio                                                                            H H H Cu                                                                              I  2 2 2 1 0 0                       2-63                                                                             ethyl     ethyl     8-ureido  H H H Cu                                                                              BF.sub.4                                                                         2 2 2 1 0 0                       __________________________________________________________________________

                                      TABLE 14                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                           R.sup.2                                                                           R.sup.3  R.sup.4       R.sup.7                                                                         R.sup.8                                                                         M X  i j k l m o                        __________________________________________________________________________    2-64                                                                             n-butyl                                                                           n-butyl                                                                           8-N-n-propylureido                                                                     H             H H Cu                                                                              PF.sub.6                                                                         2 2 2 1 0 0                        2-65                                                                             ethyl                                                                             ethyl                                                                             8-N,N-diethylureido                                                                    H             H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        2-66                                                                             ethyl                                                                             ethyl                                                                             8-thioureido                                                                           H             H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                        2-67                                                                             ethyl                                                                             ethyl                                                                             8-N-acetyl-N-                                                                          H             H H Cu                                                                              SbF.sub.6                                                                        2 2 2 1 0 0                                   phenylthioureido                                                   2-68                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-acetyl      H H Cu                                                                              ClO.sub.4                                                                        2 3 2 1 1 0                        2-69                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-isovaleryl  H H Cu                                                                              ClO.sub.4                                                                        2 3 2 1 1 0                        2-70                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-stearoyl    H H Cu                                                                              ClO.sub.4                                                                        2 3 2 1 1 0                        2-71                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-benzoyl     H H Cu                                                                              ClO.sub.4                                                                        2 3 2 1 1 0                        2-72                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(1-naphthoyl)                                                                             H H Cu                                                                              ClO.sub.4                                                                        2 3 2 1 1 0                        2-73                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-carboxy     H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        2-74                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-N-phenylcarbamoyl                                                                         H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        2-75                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-N-methylcarbamoyl                                                                         H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        2-76                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-N-ethoxy-methylcarbamoyl                                                                  H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        2-77                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-2-oxolanyl-                                                                            H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                            methylcarbamoyl)                                          2-78                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-N-allylcarbamoyl                                                                          H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        2-79                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-3-(2-methoxycarbonyl)-                                                                 H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                            thienylcarbamoyl)                                         2-80                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-N-2-thiazolylcarbamoyl                                                                    H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        2-81                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-2-benzoimidazolyl                                                                      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                            carbamoyl)                                                2-82                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-2-benzoxazolylcarbamoyl)                                                               H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        2-83                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-2-benzothioazolyl-                                                                     H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                            carbamoyl)                                                2-84                                                                             ethyl                                                                             ethyl                                                                             8-methyl 1-(N-2-pyridylcarbamoyl)                                                                    H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                        __________________________________________________________________________

                                      TABLE 15                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4      R.sup.7                                                                         R.sup.8                                                                         M X  i j k l m o                               __________________________________________________________________________    2-85                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-4-pyrimidylcarbamoyl)                                                                 H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-86                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-quinolylcarbamoyl)                                                                  H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-87                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-3H-indo-2-lylcarbamoyl)                                                               H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-88                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-sulfo      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-89                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-phenylsulfamoyl                                                                        H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-90                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-methylsulfamoyl                                                                        H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-91                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-ethoxymethylsulfamoyl                                                                  H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-92                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-oxolanylmethyl-                                                                     H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                             sulfamoyl)                                                      2-93                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-allylsulfamoyl                                                                         H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-94                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-thienylsulfamoyl)                                                                   H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-95                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-thiazolylsulfamoyl)                                                                 H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-96                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-benzoimidazolyl-                                                                    H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                             sulfamoyl)                                                      2-97                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                             benzoxazolylsulfamoyl)                                          2-98                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                                             benzothiazolylsulfamoyl)                                        2-99                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-pyridylsulfamoyl)                                                                   H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-100                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-4-pyrimidylsulfamoyl)                                                                 H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-101                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-quinoiylsulfamoyl)                                                                  H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-102                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-3H-indo-2-lylsulfamoyl)                                                               H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-103                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-methoxycarbonyl                                                                          H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-104                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-ethoxycarbonyl                                                                           H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-105                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-n-butoxycarbonyl                                                                         H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               __________________________________________________________________________

                                      TABLE 16                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4      R.sup.7                                                                         R.sup.8                                                                         M X  i j k l m o                               __________________________________________________________________________    2-106                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-lauryloxycarbonyl                                                                        H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-107                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-stearyloxycarbonyl                                                                       H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-108                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-phenoxycarbonyl                                                                          H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-109                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-p-tolyloxycarbonyl                                                                       H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-110                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-p-chlorophenoxycarbonyl                                                                  H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-111                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-p-methoxyphenocarbonyl                                                                   H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-112                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-nitro      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-113                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-nitro      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-114                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-methyl     H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-117                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-chloro     H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-118                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-chloro     H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-119                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-bromo      H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-120                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-fluoro     H H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 1 0                               2-121                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H            Ph                                                                              H Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                               __________________________________________________________________________

                                      TABLE 17                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4                                                                         R.sup.7                                                                         R.sup.8  M X  i j k l m o                                   __________________________________________________________________________    2-128                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-chloro Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   2-129                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-chloro Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   2-130                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-chloro Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   2-131                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-fluoro Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   2-133                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-phenyl Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   2-140                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-methoxycarbonyl                                                                      Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   2-141                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-ethoxycarbonyl                                                                       Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   2-142                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-cyano  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   2-143                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-trifluoremethyl                                                                      Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   2-144                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-trifluoremethyl                                                                      Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   2-147                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-nitro  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                   __________________________________________________________________________

                                      TABLE 18                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4                                                                         R.sup.7                                                                         R.sup.8     M X  i j k l m o                                __________________________________________________________________________    2-148                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-carboxyl  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-149                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-carboxyl  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-150                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-phenoxycarbony1                                                                         Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-151                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-p-tolyloxycarbony1                                                                      Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-152                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-o-        Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                  bromophenoxycarbony1                                        2-153                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-acetly    Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-154                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-propiony1 Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-155                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-isovalery1                                                                              Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-156                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-stearoy1  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-157                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-benzoy1   Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-158                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-phenylcarbamoy1                                                                       Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-159                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-N-methylcarbamoy1                                                                       Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-160                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-N-allylcarbamoy1                                                                        Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-161                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-thienylcarbamoyl)                                                                  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0                                  2-162                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-        Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                  benzothiazolylcarbamoy1                                     2-163                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-pyridylcarbamoyl)                                                                  Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-164                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-3H-indo-2-                                                                           Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                  lylcarbamoyl)                                               2-165                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-phenylsulfamoy1                                                                       Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-166                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-methylsulfamoy1                                                                       Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                2-167                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-(N-2-     Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                  oxolanylmethylsulfamoyl)                                    2-168                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-     Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                                                  thiazolylsulfamoyl)                                         __________________________________________________________________________

                                      TABLE 19                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4                                                                         R.sup.7 R.sup.8        M X  i j k l m o                       __________________________________________________________________________    2-169                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H       4-N-benzoimidazolylsulfamoyl                                                                 Ni                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                       2-170                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H       6-(N-2-pyrimidylsulfamoyl)                                                                   Fe                                                                              ClO.sub.4                                                                        2 2 2 1 0 1                       2-171                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H F       H              Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-172                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H C1      H              Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-173                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H Br      H              Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-176                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H cyano   H              Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-179                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H o-hydroxyphenyl                                                                       H              Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-180                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H 3-pyridinyl                                                                           H              Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-188                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H formyl  H              Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       2-189                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H acetyl  H              Cu                                                                              ClO.sub.4                                                                        2 2 2 1 0 0                       __________________________________________________________________________

                                      TABLE 20                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                             R.sup.2                                                                             R.sup.3                                                                         R.sup.4                                                                         R.sup.7      R.sup.8                                                                         M X  i j k l m o                            __________________________________________________________________________    2-190                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H hydroxyiminomethylcarbonyl                                                                 H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-191                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H bromolacetyl H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-192                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H bydroxycarbonyl                                                                            H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-193                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H methoxycarbonyl                                                                            H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-194                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H n-hexylcarbonyl                                                                            H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            2-195                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H aminothiocarbonyl                                                                          H Cu                                                                              ClO.sub.4                                                                        2 2 2 0 0 0                            __________________________________________________________________________

Next, the process for producing new indoaniline metal complexesaccording to the present invention will be described. The newindoaniline metal complexes represented by the general formula (1) or(2) can be synthesized by modifying the method described in JapaneseLaid-Open (ko-kai) No. 227569/1988. That is, for 4-hydroxyphenanthridinederivative represented by the following general formula (6) ##STR6## (inthe formula, R⁴, R⁵, R⁶, m and n are the same as those of the abovedefinitions, whereas R¹⁰ denotes a hydrogen atom or halogen atom) or4-hydroxyacridine derivative represented by the following generalformula (7): ##STR7## (in the formula, R⁴, R⁷, R⁸, m and n are the sameas those of the above definitions, whereas R¹¹ denotes a hydrogen atomand halogen atom), an addition reaction of a p-N,N-substituted aminoaniline compound represented by the following general formula (8):##STR8## (in the formula, R¹, R², R³ and 1 are the same as those of theabove definitions) or its chloride, sulfate, nitrate or organic acidsalt is carried out by using an oxidizing agent and a new indoanilinederivative represented by the following general formula (3): ##STR9##(in the formula, R¹, R², R³, R⁴, R⁵, R⁶, l, m and n are the same asthose of the above definitions) and a new indoaniline derivativerepresented by the following general formula (4): ##STR10## (in theformula, R¹, R², R³, R⁴, R⁷, R⁸, l, m and o are the same as those of theabove definitions) can be obtained. Then, chelate reaction with theindoaniline derivative represented by the general formula (3) or (4)mentioned above is carried out by using a metal salt represented by thefollowing general formula (9): ##STR11## (in the formula, M and X arethe same as those of the above definitions, whereas r-s denote aninteger of 1-3 and t denotes an integer of 0-20), so that a newindoaniline metal complex represented by the general formula (1) or (2)can be prepared.

Specifically, a new indoaniline derivative represented by the generalformulae (3) and (4) and a metal salt represented by the general formula(9) are allowed to react at temperatures of 0° C. to 100° C., preferably0° C. to 40° C., for a period of 10 min to 24 hr in water and a solventsuch as methanol, ethanol, isopropanol, acetone, methylethylketone,dioxane and tetrahydrofuran, preferably water and an alcohol solventsuch as methanol and ethanol. After the completion of the reaction, theprecipitated crystal is filtered out, cleaned with water and an alcoholsolvent such as methanol or ethanol and air-dried and under reducedpressure, so that a new indoaniline metal complex represented by thegeneral formula (1) or (2) can be obtained.

Hereinafter, specific examples of new indoaniline derivativesrepresented by the following general formula (3) or (4) will bementioned but the present invention is not limited to these examples. Inthe tables that follow, 1, m, n, and o are indicated as 0 (zero) wherethe appropriate R group is a hydrogen atom, i.e., 1, m, n, and o aretechnically 1 (one). ##STR12##

                                      TABLE 21                                    __________________________________________________________________________    No. R.sup.1  R.sup.2                                                                              R.sup.3                                                                            R.sup.4                                                                          R.sup.5                                                                         R.sup.6                                                                         l m o                                         __________________________________________________________________________    3-1 ethyl    ethyl  8-methyl                                                                           H  H H 1 0 0                                         3-2 ethyl    ethyl  H    H  R H 0 0 0                                         3-3 methyl   methyl H    H  H H 0 0 0                                         3-4 n-propyl n-propyl                                                                             H    H  H H 0 0 0                                         3-5 i-propyl i-propyl                                                                             H    H  H H 0 0 0                                         3-6 n-butyl  n-butyl                                                                              H    H  H H 0 0 0                                         3-7 s-butyl  H      H    H  H H 0 0 0                                         3-8 n-pentyl n-pentyl                                                                             H    H  H H 0 0 0                                         3-9 n-hexyl  n-hexyl                                                                              H    H  H H 0 0 0                                         3-10                                                                              2-ethylhexyl                                                                           2-ethylhexyl                                                                         H    H  H H 0 0 0                                         3-11                                                                              cetyl    cetyl  H    H  H H 0 0 0                                         3-12                                                                              ethyl    2-cyanoethyl                                                                         H    H  H H 0 0 0                                         3-13                                                                              ethyl    2-chloroethyl                                                                        H    H  H H 0 0 0                                         3-14                                                                              2-ethoxyethyl                                                                          2-ehoxyethyl                                                                         H    H  H H 0 0 0                                         3-15                                                                              methoxyethoxyethyl                                                                     methoxyethoxy                                                                        H    H  H H 0 0 0                                                      ethyl                                                            3-16                                                                              benzyl   benzyl H    H  Ph                                                                              H 0 0 0                                         3-17                                                                              ethyl    benzyloxyethyl                                                                       H    H  Ph                                                                              H 0 0 0                                         3-18                                                                              ethyl    methylcarbonyl                                                                       H    H  Ph                                                                              H 0 0 0                                                      oxyethyl                                                         3-19                                                                              etbyl    2-phenoxyethyl                                                                       H    H  Ph                                                                              H 0 0 0                                         3-20                                                                              ethyl    2-acetoxyethyl                                                                       H    H  Ph                                                                              H 0 0 0                                         3-21                                                                              2-carboxyethyl                                                                         2-carboxyethyl                                                                       H    H  H H 0 0 0                                         __________________________________________________________________________

                                      TABLE 22                                    __________________________________________________________________________    No.                                                                              R.sup.1   R.sup.2   R.sup.3                                                                              R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         l m o                                     __________________________________________________________________________    3-22                                                                             ethoxycarbonylmethyl                                                                    ethoxycarbonylmethyl                                                                    H      H H H 0 0 0                                     3-23                                                                             3-mesylpropyl                                                                           3-mesylpropyl                                                                           H      H H H 0 0 0                                     3-24                                                                             ethyl     2-oxolanylmethyl                                                                        H      H H H 0 0 0                                     3-25                                                                             H         phenyl    H      H H H 0 0 0                                     3-26                                                                             H         p-tolyl   H      H H H 0 0 0                                     3-27                                                                             H         p-chlorophenyl                                                                          H      H H H 0 0 0                                     3-28                                                                             H         p-methoxyphenyl                                                                         H      H H H 0 0 0                                     3-29                                                                             H         p-n-butoxyphenyl                                                                        H      H H H 0 0 0                                     3-30                                                                             2-propenyl                                                                              2-propenyl                                                                              H      H H H 0 0 0                                     3-31                                                                             ethyl     2-methyl-2-propenyl                                                                     H      H H H 0 0 0                                     3-32                                                                             ethyl     2-chloro-2-propenyl                                                                     H      H H H 0 0 0                                     3-33                                                                             ethyl     cyclohexyl                                                                              H      H H H 0 0 0                                     3-34                                                                             piperidinyl         H      H H H 0 0 0                                     3-35                                                                             morpholinyl         H      H H H 0 0 0                                     3-38                                                                             ethyl     ethyl     8-ethyl                                                                              H H H 1 0 0                                     3-39                                                                             ethyl     ethyl     8-cyclohexyl                                                                         H H H 1 0 0                                     3-41                                                                             ethyl     ethyl     8-(2-propenyl)                                                                       H H H 1 0 0                                     3-42                                                                             ethyl     ethyl     8-benzyl                                                                             H H H 1 0 0                                     __________________________________________________________________________

                                      TABLE 23                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                              R.sup.2                                                                              R.sup.3   R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         l m o                                        __________________________________________________________________________    3-43                                                                             ethyl  ethyl  8-methoxy H H H 1 0 0                                        3-44                                                                             2-phenoxyethyl                                                                       2-phenoxyethyl                                                                       8,10-diethoxy                                                                           H H H 2 0 0                                        3-45                                                                             2-ethoxyethyl                                                                        2-ethoxyethyl                                                                        8-methoxy-10-                                                                           H H H 2 0 0                                                         methyl                                                       3-49                                                                             n-butyl                                                                              n-butyl                                                                              8-diethylamino                                                                          H H H 1 0 0                                        3-50                                                                             n-butyl                                                                              n-butyl                                                                              8-diisopropylamino                                                                      H H H 1 0 0                                        3-51                                                                             n-butyl                                                                              n-butyl                                                                              8-tosylamino                                                                            H H H 1 0 0                                        3-52                                                                             ethyl  ethyl  8-mesylamino                                                                            H 11                                                                              H 1 0 0                                        3-53                                                                             n-butyl                                                                              n-butyl                                                                              8-laurloyamino                                                                          H H H 1 0 0                                        3-54                                                                             ethyl  ethyl  8-palmitoylamino                                                                        H H H 1 0 0                                        3-55                                                                             ethyl  ethyl  8-stearoylamino                                                                         H H H 1 0 0                                        3-56                                                                             ethyl  ethyl  8-(1-naphtoyl)amino                                                                     H H H 1 0 0                                        3-59                                                                             ethyl  ethyl  8-n-butylthio                                                                           H H H 1 0 0                                        3-60                                                                             n-butyl                                                                              n-butyl                                                                              8-phenylthio                                                                            H H H 1 0 0                                        3-61                                                                             ethyl  ethyl  8-p-chlorophenylthio                                                                    H H H 1 0 0                                        3-62                                                                             n-butyl                                                                              n-butyl                                                                              8-benzylthio                                                                            H H H 1 0 0                                        3-63                                                                             ethyl  ethyl  8-ureido  H H H 1 0 0                                        __________________________________________________________________________

                                      TABLE 24                                    __________________________________________________________________________    No. R.sup.1                                                                           R.sup.2                                                                           R.sup.3       R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         l m o                                         __________________________________________________________________________    3-64                                                                              n-butyl                                                                           n-butyl                                                                           8-N-n-propylureido                                                                          H H H 1 0 0                                         3-65                                                                              ethyl                                                                             ethyl                                                                             8-N,N-diethylureido                                                                         H H H 1 0 0                                         3-66                                                                              ethyl                                                                             ethyl                                                                             8-thioreido   H H H 1 0 0                                         3-67                                                                              ethyl                                                                             ethyl                                                                             8-N-acetyl-N-phenylthioureido                                                               H H H 1 0 0                                         __________________________________________________________________________

                                      TABLE 25                                    __________________________________________________________________________    No. R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4        R.sup.5                                                                         R.sup.6                                                                         l m o                                       __________________________________________________________________________    3-85                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-pyrimidylcarbamoyl)                                                                   H H 1 1 0                                       3-86                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-quinolylcarbamoyl)                                                                    H H 1 1 0                                       3-87                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-3H-indo-2-lylcarbamoyl)                                                                 H H 1 1 0                                       3-88                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-sulfo        H H 1 1 0                                       3-89                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-phenylsulfamoyl                                                                          H H 1 1 0                                       3-90                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-methylsulfamoyl                                                                          H H 1 1 0                                       3-91                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-ethoxymethylsulfamoyl                                                                    H H 1 1 0                                       3-92                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-oxolanylmethylsulfamoyl)                                                              H H 1 1 0                                       3-93                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-allylsulfamoyl                                                                           H H 1 1 0                                       3-94                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-thienylsulfamoyl)                                                                     H H 1 1 0                                       3-95                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-thiazolylsulfamoyl)                                                                   H H 1 1 0                                       3-96                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-benzoimidazolylsulfamoyl)                                                             H H 1 1 0                                       3-97                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-benzoxazolylsulfamoyl)                                                                H H 1 1 0                                       3-98                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-benzothiazolylsulfamoyl)                                                              H H 1 1 0                                       3-99                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-pyridylsulfamoyl)                                                                     H H 1 1 0                                        3-100                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-pyrimidylsulfamoyl)                                                                   H H 1 1 0                                        3-101                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-quinolylsulfamoyl)                                                                    H H 1 1 0                                        3-102                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           l-(N-3H-indo-2-lylsulfamoy-)                                                                 H H 1 1 0                                        3-103                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-methoxycarbonyl                                                                            H H 1 1 0                                        3-104                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-ethoxycarbonyl                                                                             H H 1 1 0                                        3-105                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-n-butoxycarbonyl                                                                           H H 1 1 0                                       __________________________________________________________________________

                                      TABLE 26                                    __________________________________________________________________________    No. R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4      R.sup.5                                                                         R.sup.6                                                                         l m o                                         __________________________________________________________________________    3-106                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-lauryloxycarbonyl                                                                        H H 1 1 0                                         3-107                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-stearyloxycarbonyl                                                                       H H 1 1 0                                         3-108                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-phenoxycarbonyl                                                                          H H 1 1 0                                         3-109                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-p-tolyloxycarbonyl                                                                       H H 1 1 0                                         3-110                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-o-chlorophenoxycarbonyl                                                                  H H 1 1 0                                         3-111                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-o-methoxyphenocarbonyl                                                                   H H 1 1 0                                         3-112                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-nitro      H H 1 1 0                                         3-113                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-nitro      H H 1 1 0                                         3-117                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-chloro     H H 1 1 0                                         3-118                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-chloro     H H 1 1 0                                         3-119                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-bromo      H H 1 1 0                                         3-120                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           2-fluoro     H H 1 1 0                                         3-121                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                           H            Ph                                                                              H 1 0 0                                         __________________________________________________________________________

                  TABLE 27                                                        ______________________________________                                        No.  R.sup.1                                                                              R.sup.2                                                                              R.sup.3                                                                              R.sup.4                                                                           R.sup.5                                                                           R.sup.6  l   m   o                          ______________________________________                                        3-127                                                                              ethyl  ethyl  8-methyl                                                                             H   H   4-chloro 1   0   1                          3-128                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-chloro 1   0   1                          3-129                                                                              ethyl  ethyl  8-methyl                                                                             H   H   6-chloro 1   0   1                          3-131                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-fluoro 1   0   1                          3-133                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-phenyl 1   0   1                          3-140                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-methoxy-                                                                             1   0   1                                                            carbonyl                                    3-141                                                                              ethyl  ethyl  8-methyl                                                                             H   H   6-ethoxy-                                                                              1   0   1                                                            carbonyl                                    3-143                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-trifluore-                                                                           1   0   1                                                            methyl                                      3-144                                                                              ethyl  ethyl  8-methyl                                                                             H   H   6-trifluore-                                                                           1   0   1                                                            methyl                                      3-146                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-nitro  1   0   1                          3-147                                                                              ethyl  ethyl  8-methyl                                                                             H   H   6-nitro  1   0   1                          ______________________________________                                    

                                      TABLE 28                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4                                                                         R.sup.5                                                                         R.sup.6        l m o                                        __________________________________________________________________________    3-148                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-carboxyl     1 0 1                                        3-149                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-carboxyl     1 0 1                                        3-150                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-phenoxycarbonyl                                                                            1 0 1                                        3-151                                                                            ethyl                                                                            ethyl                                                                            8-niethyl                                                                          H H 4-p-tolyloxycarbonyl                                                                         1 0 1                                        3-152                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-o-bromophenoxycarbonyl                                                                     1 0 1                                        3-153                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-acetyl       1 0 1                                        3-154                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-propionyl    1 0 1                                        3-155                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-isovaleryl   1 0 1                                        3-156                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-stearoyl     1 0 1                                        3-157                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-benzoyl      1 0 1                                        3-158                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-phenylcarbamoyl                                                                          1 0 1                                        3-159                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-N-methylcarbamoyl                                                                          1 0 1                                        3-160                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-N-allylcarbamoyl                                                                           1 0 1                                        3-161                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-thienylcarbamoyl)                                                                     1 0 1                                        3-162                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-benzothiazolylcarbamoyl                                                                  1 0 1                                        3-163                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-pyridylcarbamoyl)                                                                     1 0 1                                        3-164                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-3H-indo-2-lylcarbamoyl)                                                                 1 0 1                                        3-165                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-phenylsulfamoyl                                                                          1 0 1                                        3-166                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-methylsulfamoyl                                                                          1 0 1                                        3-167                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-(N-2-oxolanylmethylsulfamoyl)                                                              1 0 1                                        3-168                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-thiazolylsulfamoyl)                                                                   1 0 1                                        __________________________________________________________________________

                                      TABLE 29                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4                                                                         R.sup.5 R.sup.6       l m o                                   __________________________________________________________________________    3-169                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H       4-N-benzoimidazolylsulfamoyl                                                                1 0 1                                   3-170                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H       6-(N-2-pyrimidylsulfamoyl)                                                                  1 0 1                                   3-171                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H F       H             1 0 0                                   3-172                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H Cl      H             1 0 0                                   3-173                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H Br      H             1 0 0                                   3-176                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H cyano   H             1 0 0                                   3-179                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H o-hydroxyphenyl                                                                       H             1 0 0                                   3-180                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H 3-pyridinyl                                                                           H             1 0 0                                   3-188                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H formyl  H             1 0 0                                   3-189                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H acetyl  H             1 0 0                                   __________________________________________________________________________

                                      TABLE 30                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                             R.sup.2                                                                             R.sup.3                                                                         R.sup.4                                                                         R.sup.5      R.sup.6                                                                         l m o                                       __________________________________________________________________________    3-190                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H hydroxyiminomethylcarbonyl                                                                 H 0 0 0                                       3-191                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H bromoacetyl  H 0 0 0                                       3-192                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H hydroxycarbonyl                                                                            H 0 0 0                                       3-193                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H methoxycarbonyl                                                                            H 0 0 0                                       3-194                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H n-hexylcarbonyl                                                                            H 0 0 0                                       3-195                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H aminothioarbonyl                                                                           H 0 0 0                                       __________________________________________________________________________     ##STR13##                                                                 

                                      TABLE 31                                    __________________________________________________________________________    No.                                                                              R.sup.1  R.sup.2    R.sup.3                                                                            R.sup.4                                                                         R.sup.7                                                                         R.sup.8                                                                         l m o                                       __________________________________________________________________________    4-1                                                                              ethyl    ethyl      8-methyl                                                                           H H H 1 0 0                                       4-2                                                                              ethyl    ethyl      H    H H H 0 0 0                                       4-3                                                                              methyl   methyl     H    H H H 0 0 0                                       4-4                                                                              n-propyl n-propyl   H    H H H 0 0 0                                       4-5                                                                              i-propyl i-propyl   H    H H H 0 0 0                                       4-6                                                                              n-butyl  n-butyl    H    H H H 0 0 0                                       4-7                                                                              s-butyl  H          H    H H H 0 0 0                                       4-8                                                                              n-pentyl n-pentyl   H    H H H 0 0 0                                       4-9                                                                              n-heyxl  n-hexyl    H    H H H 0 0 0                                       4-10                                                                             2-ethylhexyl                                                                           2-ethylhexyl                                                                             H    H H H 0 0 0                                       4-11                                                                             cetyl    cetyl      H    H H H 0 0 0                                       4-12                                                                             ethyl    2-cyanoethyl                                                                             H    H H H 0 0 0                                       4-13                                                                             ethyl    2-chloroethyl                                                                            H    H H H 0 0 0                                       4-14                                                                             2-ethoxyethyl                                                                          2-ethoxyethyl                                                                            H    H H H 0 0 0                                       4-15                                                                             methoxyethoxyethyl                                                                     methoxyethoxyethyl                                                                       H    H H H 0 0 0                                       4-16                                                                             benzyl   benzyl     H    H Ph                                                                              H 0 0 0                                       4-17                                                                             ethyl    benzyloxyethyl                                                                           H    H Ph                                                                              H 0 0 0                                       4-18                                                                             ethyl    methylcarbonyloxyethyl                                                                   H    H Ph                                                                              H 0 0 0                                       4-19                                                                             ethyl    2-phenoxyethyl                                                                           H    H Ph                                                                              H 0 0 0                                       4-20                                                                             ethyl    2-acetoxyethyl                                                                           H    H Ph                                                                              H 0 0 0                                       4-21                                                                             2-caboxyethyl                                                                          2-caboxyethyl                                                                            H    H H H 0 0 0                                       __________________________________________________________________________

                                      TABLE 32                                    __________________________________________________________________________    No.                                                                              R.sup.1   R.sup.2   R.sup.3                                                                              R.sup.4                                                                         R.sup.7                                                                         R.sup.8                                                                         l m o                                     __________________________________________________________________________    4-22                                                                             ethoxycabonylmethyl                                                                     ethoxycabonylmethyl                                                                     H      H H H 0 0 0                                     4-23                                                                             3-mesylpropyl                                                                           3-mesylpropyl                                                                           H      H H H 0 0 0                                     4-24                                                                             ethyl     2-oxolanylmethyl                                                                        H      H H H 0 0 0                                     4-25                                                                             H         phenyl    H      H H H 0 0 0                                     4-26                                                                             H         p-tolyl   H      H H H 0 0 0                                     4-27                                                                             H         p-chlorophenyl                                                                          H      H H H 0 0 0                                     4-28                                                                             H         p-methoxyphenyl                                                                         H      H H H 0 0 0                                     4-29                                                                             H         p-n-butoxyphenyl                                                                        H      H H H 0 0 0                                     4-30                                                                             2-propenyl                                                                              2-propenyl                                                                              H      H H H 0 0 0                                     4-31                                                                             ethyl     2-methyl-2-propenyl                                                                     H      H H H 0 0 0                                     4-32                                                                             ethyl     2-chloro-2-propenyl                                                                     H      H H H 0 0 0                                     4-33                                                                             ethyl     cyclohexyl                                                                              H      H H H 0 0 0                                     4-34                                                                             piperidinyl         H      H H H 0 0 0                                     4-35                                                                             morpholinyl         H      H H H 0 0 0                                     4-38                                                                             ethyl     ethyl     8-ethyl                                                                              H H H 1 0 0                                     4-39                                                                             ethyl     ethyl     8-cyclohexyl                                                                         H H H 1 0 0                                     4-41                                                                             ethyl     ethyl     8-(2-propenyl)                                                                       H H H 1 0 0                                     4-42                                                                             ethyl     ethyl     8-benzyl                                                                             H H H 1 0 0                                     __________________________________________________________________________

                                      TABLE 33                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                              R.sup.2                                                                              R.sup.3   R.sup.4                                                                         R.sup.7                                                                         R.sup.8                                                                         l m o                                        __________________________________________________________________________    4-43                                                                             ethyl  ethyl  8-methoxy H H H 1 0 0                                        4-44                                                                             2-phenoxyethyl                                                                       2-phenoxyethyl                                                                       8,10-diethoxy                                                                           H H H 2 0 0                                        4-45                                                                             2-ethoxyethyl                                                                        2-ethoxyethyl                                                                        8-methoxy-10-methyl                                                                     H H H 2 0 0                                        4-49                                                                             n-butyl                                                                              n-butyl                                                                              8-diethylamino                                                                          H H H 1 0 0                                        4-50                                                                             n-butyl                                                                              n-butyl                                                                              8-diisopropylamino                                                                      H H H 1 0 0                                        4-51                                                                             n-butyl                                                                              n-butyl                                                                              8-tosylamino                                                                            H H H 1 0 0                                        4-52                                                                             ethyl  ethyl  8-mesylamino                                                                            H H H I 0 0                                        4-53                                                                             n-butyl                                                                              n-butyl                                                                              8-laurolyamino                                                                          H H H I 0 0                                        4-54                                                                             ethyl  ethyl  8-palrmitoylamino                                                                       H H H 1 0 0                                        4-55                                                                             ethyl  ethyl  8-stearoylamino                                                                         H H H 1 0 0                                        4-56                                                                             ethyl  ethyl  8-(1-naphthoyl)amino                                                                    H H H I 0 0                                        4-57                                                                             2-ethylhexyl                                                                         2-ethylhexyl                                                                         8-methyl  H H H 1 0 0                                        4-58                                                                             2-ethylhexyl                                                                         2-ethylhexyl                                                                         8-methylthio                                                                            H H H 1 0 0                                        4-59                                                                             ethyl  ethyl  8-n-butylthio                                                                           H H H I 0 0                                        4-60                                                                             n-butyl                                                                              n-butyl                                                                              8-phenylthio                                                                            H H H 1 0 0                                        4-61                                                                             ethyl  ethyl  8-p-chlorophenylthio                                                                    H H H 1 0 0                                        4-62                                                                             n-butyl                                                                              n-butyl                                                                              8-benzylthio                                                                            H H H 1 0 0                                        4-63                                                                             ethyl  ethyl  8-ureido  H H H 1 0 0                                        __________________________________________________________________________

                                      TABLE 34                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                           R.sup.2                                                                           R.sup.3       R.sup.4             R.sup.7                                                                         R.sup.8                                                                         l m o                        __________________________________________________________________________    4-64                                                                             n-butyl                                                                           n-butyl                                                                           8-N-n-propylureido                                                                          H                   H H 1 0 0                        4-65                                                                             ethyl                                                                             ethyl                                                                             8-N,N-diethylureido                                                                         H                   H H 2 0 0                        4-66                                                                             ethyl                                                                             ethyl                                                                             8-thioureido  H                   H H 2 0 0                        4-67                                                                             ethyl                                                                             ethyl                                                                             8-N-acetyl-N-phenylthioureido                                                               H                   H H 2 0 0                        4-68                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-acetyl            H H 2 0 0                        4-69                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-isovaleryl        H H 1 0 0                        4-70                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-stearoyl          H H 1 0 0                        4-71                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-benzoyl           H H 1 0 0                        4-72                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-(1-naphthoyl)     H H 1 0 0                        4-73                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-carboxy           H H 1 0 0                        4-74                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-N-phenylcarbamoyl H H 1 0 0                        4-75                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-N-methylcarbamoyl H H 1 0 0                        4-76                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-N-ethoxymethylcarbamoyl                                                                         H H 1 0 0                        4-77                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-(N-2-oxolanylmethylcarbamoyl)                                                                   H H 1 0 0                        4-78                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-N-allylcarbamoyl  H H 1 0 0                        4-79                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-(N-3-(2-methoxycarbonyl)thienylcarbamoyl)                                                       H H 1 0 0                        4-80                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-N-2-thiazolylcarbamoyl                                                                          H H 1 0 0                        4-81                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-(N-2-benzoimidazolylcarbamoyl)                                                                  H H 1 0 0                        4-82                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-(N-2-benzoxazolylcarbamoyl)                                                                     H H 1 0 0                        4-83                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-(N-2-benzothioazolyl-carbamoyl)                                                                 H H 1 0 0                        4-84                                                                             ethyl                                                                             ethyl                                                                             8-methyl      1-(N-2-pyridylcarbamoyl)                                                                          H H 1 0 0                        __________________________________________________________________________

                                      TABLE 35                                    __________________________________________________________________________    No. R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4        R.sup.7                                                                         R.sup.8                                                                         l m o                                       __________________________________________________________________________    4-85                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-4-pyrimidylcarbamoyl)                                                                   H H 1 1 0                                       4-86                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-quinolylcarbamoyl)                                                                    H H 1 1 0                                       4-87                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-3H-indo-2-lylcarbamoyl)                                                                 H H 1 1 0                                       4-88                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-sulfo        H H 1 1 0                                       4-89                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-phenylsulfamoyl                                                                          H H 1 1 0                                       4-90                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-methylsulfamoyl                                                                          H H 1 1 0                                       4-91                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-ethoxymethylsulfamoyl                                                                    H H 1 1 0                                       4-92                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-oxolanylmethylsulfamoyl)                                                              H H 1 1 0                                       4-93                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-N-allylsulfamoyl                                                                           H H 1 1 0                                       4-94                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-thienylsulfamoyl)                                                                     H H 1 1 0                                       4-95                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-thiazolylsulfamoyl)                                                                   H H 1 1 0                                       4-96                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-benzoimidazolylsulfamoyl)                                                             H H 1 1 0                                       4-97                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-benzoxazolylsulfamoyl)                                                                H H 1 1 0                                       4-98                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-benzothiazolylsulfamoyl)                                                              H H 1 1 0                                       4-99                                                                              ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-pyridylsulfamoyl)                                                                     H H 1 1 0                                        4-100                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-4-pyrimidylsulfamoyl)                                                                   H H 1 1 0                                        4-101                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-2-quinolylsulfamoyl)                                                                    H H 1 1 0                                        4-102                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-(N-3H-indo-2-lylsulfamoyl)                                                                 H H 1 1 0                                        4-103                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-methoxycarbonyl                                                                            H H 1 1 0                                        4-104                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-ethoxycarbonyl                                                                             H H 1 1 0                                        4-105                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           1-n-butoxycarbonyl                                                                           H H 1 1 0                                       __________________________________________________________________________

                                      TABLE 36                                    __________________________________________________________________________    No. R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                             R.sup.4     R.sup.7                                                                         R.sup.8                                                                         l  m o                                        __________________________________________________________________________    4-106                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            1-lauryloxycarbonyl                                                                       H H 1  1 0                                        4-107                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            1-stearyloxycarbonyl                                                                      H H 1  1 0                                        4-108                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            1-phenoxycarbonyl                                                                         H H 1  1 0                                        4-109                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            1-p-tolyloxycarbonyl                                                                      H H 1  1 0                                        4-110                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            1-p-chlorophenoxycarbonyl                                                                 H H 1  1 0                                        4-111                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            1-p-methoxyphenocarbonyl                                                                  H H 1  1 0                                        4-112                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            1-nitro     H H 1  1 0                                        4-113                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            2-nitro     H H 1  1 0                                        4-117                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            1-chloro    H H 1  1 0                                        4-118                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            2-chloro    H H 1  1 0                                        4-119                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            2-bromo     H H 1  1 0                                        4-120                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            2-fluoro    H H 1  1 0                                        4-121                                                                             ethyl                                                                            ethyl                                                                            8-methyl                                                                            H           Ph                                                                              H 1  0 0                                        __________________________________________________________________________

                  TABLE 37                                                        ______________________________________                                        No.  R.sup.1                                                                              R.sup.2                                                                              R.sup.3                                                                              R.sup.4                                                                           R.sup.7                                                                           R.sup.8  l   m   o                          ______________________________________                                        4-127                                                                              ethyl  ethyl  8-methyl                                                                             H   H   4-chloro 1   0   1                          4-128                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-chloro 1   0   1                          4-129                                                                              ethyl  ethyl  8-methyl                                                                             H   H   6-chloro 1   0   1                          4-130                                                                              ethyl  ethyl  8-methyl                                                                             H   H   7-chloro 1   0   1                          4-131                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-fluoro 1   0   1                          4-133                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-phenyl 1   0   1                          4-140                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-methoxy-                                                                             1   0   1                                                            carbonyl                                    4-141                                                                              ethyl  ethyl  8-methyl                                                                             H   H   7-ethoxy-                                                                              1   0   1                                                            carbonyl                                    4-142                                                                              ethyl  ethyl  8-methyl                                                                             H   H   7-cyano  1   0   1                          4-143                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-trifluore-                                                                           1   0   1                                                            methyl                                      4-144                                                                              ethyl  ethyl  8-methyl                                                                             H   H   6-trifluore-                                                                           1   0   1                                                            methyl                                      4-146                                                                              ethyl  ethyl  8-methyl                                                                             H   H   5-nitro  1   0   1                          4-147                                                                              ethyl  ethyl  8-methyl                                                                             H   H   6-nitro  1   0   1                          ______________________________________                                    

                                      TABLE 38                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4                                                                         R.sup.7                                                                         R.sup.8        l m o                                        __________________________________________________________________________    4-148                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-carboxyl     1 0 1                                        4-149                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-carboxyl     1 0 1                                        4-150                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-phenoxycarbonyl                                                                            1 0 1                                        4-151                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-p-tolyloxycarbonyl                                                                         1 0 1                                        4-152                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-o-bromophenoxycarbonyl                                                                     1 0 1                                        4-153                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-acetyl       1 0 1                                        4-154                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-propionyl    1 0 1                                        4-155                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-isovaleryl   1 0 1                                        4-156                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-stearoyl     1 0 1                                        4-157                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-benzoyl      1 0 1                                        4-158                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-phenylcarbamoyl                                                                          1 0 1                                        4-159                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-N-methylcarbamoyl                                                                          1 0 1                                        4-160                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 5-N-allylcarbamoyl                                                                           1 0 1                                        4-161                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-thienylcarbamoyl)                                                                     1 0 1                                        4-162                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-benzothiazolylcarbamoyl                                                                  1 0 1                                        4-163                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-pyridylcarbamoyl)                                                                     1 0 1                                        4-164                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-3H-indo-2-lylcarbamoyl)                                                                 1 0 1                                        4-165                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-phenylsulfamoyl                                                                          1 0 1                                        4-166                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-N-methylsulfamoyl                                                                          1 0 1                                        4-167                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 6-(N-2-oxolanylmethylsulfamoyl)                                                              1 0 1                                        4-168                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H 4-(N-2-thiazolylsulfamoyl)                                                                   1 0 1                                        __________________________________________________________________________

                                      TABLE 39                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                            R.sup.4                                                                         R.sup.7 R.sup.8       l m o                                   __________________________________________________________________________    4-169                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H       4-N-benzoimidazolylsulfamoyl                                                                1 0 1                                   4-170                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H H       6-(N-2-pyrimidylsulfamoyl)                                                                  1 0 1                                   4-171                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H F       H             1 0 0                                   4-172                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H Cl      H             1 0 0                                   4-173                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H Br      H             1 0 0                                   4-176                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H cyano   H             1 0 0                                   4-179                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H o-hydroxyphenyl                                                                       H             1 0 0                                   4-180                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H 3-pyridinyl                                                                           H             1 0 0                                   4-188                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H formyl  H             1 0 0                                   4-189                                                                            ethyl                                                                            ethyl                                                                            8-methyl                                                                           H acetyl  H             1 0 0                                   __________________________________________________________________________

                                      TABLE 40                                    __________________________________________________________________________    No.                                                                              R.sup.1                                                                             R.sup.2                                                                             R.sup.3                                                                         R.sup.4                                                                         R.sup.7      R.sup.8                                                                         l m o                                       __________________________________________________________________________    4-190                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H hydroxyiminomethylcarbonyl                                                                 H 0 0 0                                       4-191                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H bromoacetyl  H 0 0 0                                       4-192                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H hydroxycarbonyl                                                                            H 0 0 0                                       4-193                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H methoxycarbonyl                                                                            H 0 0 0                                       4-194                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H n-hexylcarbonyl                                                                            H 0 0 0                                       4-195                                                                            2-ethylhexyl                                                                        2-ethylhexyl                                                                        H H aminothiocarbonyl                                                                          H 0 0 0                                       __________________________________________________________________________

A process for producing new indoaniline derivatives represented by thegeneral formula (3) and (4), that is, an oxidative addition reaction ofa 4-hydroxyphenanthridine derivative represented by the general formula(6) or a 4-hydroxyacridine derivative represented by the general formula(7) with a p-N,N-substituted aminoaniline compound represented by theformula (8) or its hydrochloride, sulfate, nitrate or organic acid saltproceeds in a solvent such as water, methanol, ethanol, isopropanol,acetone, methyl ethyl ketone, dioxane or tetrahydrofuran by using anoxidizing agent such as chromic acid, lead tetraacetate, potassiumnitrosodisulfonate, ammonium peroxodisulfate,2,3-dichloro-5,6-dicyano-1,4-benzoquinone, silver nitrate, silvercarbonate, silver halogenide and ferric chloride. From the viewpoint ofoperativity in preparation, yield or ease of purification of products,ammonium peroxodisulfate or silver nitrate is preferable as an oxidizingagent. This reaction is performed at the temperature range between 0° C.and 100° C. for a period of 10 min to 24 hr. After the completion of thereaction, such operations as extraction and condensation are performedand a new indoaniline derivative represented by the general formula (3)or (4) can be prepared by using a purifying method such as columnchromatography or recrystallization if necessary.

4-hydroxyphenanthridine derivatives represented by the general formula(6) can be prepared by using the method of S. V. Kessar and others(Tetrahedron, Vol. 29, p. 177, 1973) but the present invention is notlimited to this. As a typical example, a synthetic method of4-hydroxyphenanthridine is shown below. ##STR14## STEP-1-1 (dehydrationcondensation reaction)

Under conditions: (A) initial reaction at 80° to 200° C. in a sealedtube; (B) subsequent reflux in an organic solvent such as methanol orethanol; (C) removal of the water produced at reaction temperatures of80° to 200° C. by using the Dean-Stark apparatus; and so on,o-hydroxyaniline (10) and o-chlorobenzaldehyde (11) are allowed toreact, so that anil (12) can be prepared. In preparing a derivative ofanil, the most suitable conditions of dehydration condensation reactiondepend on materials, but the condition (B) is preferable with respect toapparatus and operativity. The reaction proceeds for a period of 10 minto 24 hr, the organic solvent is removed after the completion of thereaction and the product can be purified by column chromatography,recrystallization or the like if necessary.

STEP-1-2 (ring closure reaction)

In ammonium liquor, anil (12) undergoes the ring closure reaction byusing metal potassium, so that 4-hydroxyphenanthridine (13) can beprepared. The ring closure reaction proceeds within the range between-75° C. and -30° C. for a period of 10 min to 24 hr. After thecompletion of the reaction, ammonium is removed and the obtained residuecan be purified by column chromatography, recrystallization or the likeif necessary.

4-hydroxyacridine derivatives represented by the general formula (7) canbe prepared by using the following method, but the present invention isnot limited to this. As a typical example, a synthetic method of4-hydroxyacridine is shown below. ##STR15## STEP-2-1 (Ullmann Reaction)

In the presence of a catalyst such as copper salt, o-anisidine (14),o-bromobenzoic acid (15) and potassium carbonate are allowed to reactwithout solvent or in an inactive solvent having a high boiling point,so that 2-methoxydiphenylamine-2'-carboxylic acid (16) can be obtained.In place of potassium carbonate, an inorganic base such as lithiumhydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate,sodium bicarbonate, and potassium bicarbonate, or an organic base suchas pyridine, triethylamine or dimethylaniline can be used. As thecatalyst, copper powder, copper bromide, copper iodide or copper oxidecan be used and iodine may be added as co-catalyst. The reaction canproceed without solvent, but an inactive solvent having a high-boilingpoint such as toluene, xylene, mesitylene, chlorobenzene,dichlorobenzene, bromobenzene, nitrobenzene and DMF may be added toassist the mixing. Preferably, the reaction temperature ranges from 80°C. to 200° C. and the reaction time ranges from 10 min to 24 hr.

STEP-2-2 (Ring Closure Reaction)

By reaction of 2-methoxydiphenylamine-2'-carboxylic acid (16) withphosphorus oxychloride, 4-methoxy-9-chloroacridine (17) can be obtained.Phosphorus oxychloride acts as reaction reagent, but may be used in therange of more than one equivalent to the substrate due to also acting asa solvent. Phosphorus trichloride and phosphorus pentachloride may beadded to phosphorus oxychloride as supplementary reagent. Preferably thereaction temperature ranges from 50° C. to 105° C. and the reaction timeranges from 10 min to 24 hr.

STEP-2-3 (p-toluenesulfonylhydrazide)

By reaction of 4-methoxy-9-chloroacridine (17) withp-toluenesulfonylhydrazide, N₁ -9-acridinyl-N₂-p-toluenesulfonylhydrazine (18) can be obtained. In place ofp-toluenesulfonylhydrazide, benzenesulfonylhydrazide can be employed.

STEP-2-4 (Decomposition Reaction)

By heating N₁ -9-acridinyl-N₂ -p-toluenesulfonylhydrazine (18) togetherwith alkali in ethylene glycol, 4-methoxyacridine (19) can be obtained.The reaction solvent is only required to have a boiling point higherthan 60° C. and ethanol, propanol, butanol, propylene glycol, glyceroland so on can be used in place of ethylene glycol. As alkali, aninorganic base such as lithium hydroxide, sodium hydroxide, potassiumhydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate orpotassium bicarbonate is preferable. Preferably the reaction temperatureranges from 60° C. to 150° C. and the reaction time ranges from 10 minto 24 hr.

STEP-2-5 (Demethylation Reaction)

By subjecting 4-methoxyacridine (19) to demethylation reaction,4-hydroxyacridine (20) can be obtained. As a demethylation reactionreagent, hydrobromic acid, hydroiodic acid, aluminum chloride, aluminumbromide, pyridine hydrochloride, boron trichloride, boron tribromide andboron triiodide can be used but the reagent is not limited to these. Thereaction temperature and reaction time depend on reaction reagents, but,when using hydrobromic acid as a reagent, for example, a preferablereaction temperature is in the range of 90°-120° C. and a preferablereaction time is in the range of 10 min to 24 hr. A preferable quantityof a reagent is in the range of 1-20 equivalent to the substrate. Apreferable reaction solvent is inactive to the reaction reagentmentioned above. A liquid reaction reagent, if employed, will be capableof acting also as a solvent. The transparent recording medium, preparedusing a new indoaniline metal complex according to the presentinvention, basically comprises a substrate and a recording layer, saidrecording layer comprising a developer represented by the generalformula (5), a metal salt of an organic acid or a leuco dye whichdevelops a color by reacting with said developer and a light-absorbingmaterial containing a new indoaniline metal complex represented by thegeneral formula (1) or the general formula (2) for absorbing andconverting near-infrared rays into heat, and further, depending on theuse of the medium, an underlayer is provided between the substrate andthe recording layer or a protective layer is provided on the recordinglayer.

Materials of substrates employed in the present invention are generalrecording-medium-supporting members such as glass and plastic, butplastic is preferable with respect to various aspects. Plastic materialsinclude acrylic resin, polyester resin, polymethacrylic resin, polyvinylacetate resin, polyvinyl chloride resin, nitrocellulose, polyethyleneresin, polypropylene resin, polystyrene resin, polycarbonate resin,polyimide resin, epoxy resin and polysulfone resin, among which thoseshaped in film, sheet or plate, resistant to heat and high intransparency are preferable.

Preferable developers employed in the present invention are compoundsrepresented by the following general formula (5): ##STR16## (here, X:COO, CONH and SO₂ ; A: substituted or non-substituted alkyl group,cycloalkyl group, vinyl group, allyl group, aryl group, benzyl group andnaphthyl group; R: either N-substituted carbamoyl group (CONHR¹⁰) orO-substituted oxycarbonyl (COOR¹¹); R¹⁰ and R¹¹ : substituted ornon-substituted alkyl group, cycloalkyl group, vinyl group, allyl group,aryl group, benzyl group, naphthyl group, mesyl group and tosyl group; pand q: an integer of 1-3 and p≦q).

Example of A can be given as follows: alkyl groups such as methyl,ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, lauryl, myristyl, parmityl,stearyl, behenyl, 2-hydroxyethyl, 2-cyanoethyl, 2-aminoethyl,2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl,trifluoromethyl, 2,2,2-trifluoroethyl, 2-methoxyethyl,methoxyethoxyethyl, 2-allyloxyethyl, benzyl, phenetyl, 2-benzyloxyethyl,benzylcarbonyloxymethyl, 2-phenoxyethyl, 2-acetoxyethyl, 2-carboxyethyl,ethoxycarbonylmethyl, methoxycarbonylethyl, 3-mesylpropyl, 2-furylmethyland 2-oxolanylmethyl; cycloalkyl groups such as cyclopentyl, cyclohexyland 2-methylcyclohexyl; allyl groups such as 2-propenyl, 2-butenyl,2-pentenyl, 2-hexenyl, 2-chloro-2-propenyl and 2-methyl-2-pentenyl; andaryl groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, o-chlorophenyl,m-chlorophenyl, p-chlorophenyl, o-bromophenyl, m-bromophenyl,p-bromophenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl,p-ethoxyphenyl and p-butoxyphenyl.

Examples of N-substituted carbamoyl groups can be given as follows:methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, iso-propylcarbamoyl,n-butylcarbamoyl, tert-butylcarbamoyl, n-octadecylcarbamoyl,cyclohexylcarbamoyl, allylcarbamoyl, chloromethylcarbamoyl,2-chloroethylcarbamoyl, phenylcarbamoyl, o-tolylcarbamoyl,m-tolylcarbamoyl, p-tolylcarbamoyl, naphthylcarbamoyl,o-chlorophenylcarbamoyl, m-chlorophenylcarbamoyl,p-chlorophenylcarbamoyl, 3,4-dichlorophenylcarbamoyl,o-methoxyphenylcarbamoyl, m-methoxyphenylcarbamoyl,p-methoxyphenylcarbamoyl, p-toluenesulfonylcarbamoyl, benzylcarbamoyl,α-dimethylbenzylcarbamoyl, α, α-dimethylbenzylcarbamoyl, m-methyl-α,α-dimethylbenzylcarbamoyl, m-ethyl-α, α-dimethylbenzylcarbamoyl,m-propyl-α, α-dimethylbenzylcarbamoyl and m-isopropyl-α,α-dimethylbenzylcarbamoyl.

On the other hand, examples of O-substituted oxycarbonyl groups can begiven as follows: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl,n-butoxycarbonyl, iso-butoxycarbonyl, tert-butoxycarbonyl,n-hexadecyloxycarbonyl, n-octadecyloxycarbonyl, allyloxycarbonyl,vinyloxycarbonyl, 2,2,2-trichloroethoxycarbonyl, phenoxycarbonyl,naphthyloxycarbonyl and 2-(trimethylsilyl)ethoxy carbonyl.

Organic acids for organic acid metal salts employed in the presentinvention include aliphatic carboxylic acid derivatives, benzoic acidderivatives and phthalic acid derivatives, but benzoic acid derivativesare preferable, among which o- and m-substituted benzoic acidderivatives are especially preferable, such as o-benzoylbenzoic acid,o-(2-methyl)benzoylbenzoic acid, o-(2-ethyl)benzoylbenzoic acid,o-methylbenzoic acid, m-methylbenzoic acid, o-phenylbenzoic acid,m-phenylbenzoic acid, o-tolylbenzoic acid, m-tolylbenzoic acid,o-chlorobenzoic acid, m-chlorobenzoic acid, o-bromobenzoic acid andm-bromobenzoic acid.

Preferable metals for organic acid metal salts employed in the presentinvention are iron, silver, copper, vanadium and cobalt, among whichiron is utmost preferable.

Any colorless electron-donating dye conventionally known in the field ofheat-sensitive recording paper and pressure-sensitive recording papercan be used as a leuco dye in the present invention. The followingcompounds can be given as typical examples: crystal violet lactone,3-diethylamino-6-methyl-7-anilinofluoran,3-dibutylamino-6-methyl-7-anilinofluoran,3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran,3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methyl-indol-3-yl)-4-azaphthalideand 3-(N-ethyl-N-cyclohexylamino)-6-methyl-7-anilinofluoran.

The above developers and organic acid metal salts or leuco dyes aredissolved together with a binder in an organic solvent suitable forsolvent coating, such as toluene, acetone, methyl ethyl ketone, methylisobutyl ketone and chloroform.

Examples of binders employed in the present invention can be given asfollows: polystyrene, polyvinylalcohol, polyvinylpyrrolidone,polyvinylbutyral, polyester, polycabonate, nitrocellulose, celluloseacetate, acylonitrile-butadiene-styrene resin, silicone varnish,EB-hardened resin and UV-hardened resin.

Near-infrared absorbing materials other than new indoaniline metalcomplexes according to the present invention, can also be employed inthe present invention. Any compound capable of converting near-infraredlaser rays into heat is available for a near-infrared absorbing materialin the present invention. Specific examples are immonium compounds suchas IRG002 and IRG022 (trade names; available from Nippon Kayaku K.K.),dithiol nickel complexes such as NKX-1 13, NKX-114 and NKX-1199 (tradenames; available from Nippon Kankoh-Shikiso Kenkyusho Co., Ltd.),cyanine dyes such as 1,1,5,5-tetrakis(p-dimethylaminophenyl)-3-methoxy-1, 4-pentadiene toluene and NK-2014(trade name; available from Nippon Kankoh-Shikiso Kenkyusho Co., Ltd.),squalerium dyes, naphthoquinone dyes, phthalocyanine dyes andnaphthalocyanine dyes.

For improvement in the stability and light resistance of a transparentrecording medium, singlet oxygen quenchers comprising transition metalchelate compounds such as acetylacetonate chelate, bisphenyl dithiol,salicylaldoxime, bisdithio-a-diketone may be contained withnear-infrared absorbing materials.

Recording onto a transparent recording medium according to the presentinvention can be carried out also by means of a thermal head, but moreadvantageously by means of laser rays with respect to printing speed,image resolution and the like. Employed as a laser source in the presentinvention are gas lasers such as N₂, He--Cd, Ar and He--Ne, solid laserssuch as ruby, semiconductor lasers such as Ga--As, and dye lasers, butsemiconductor lasers are preferable especially with respect to lightweight, easy handling, small size and the like. A clear record having asufficiently high recording density can be obtained on a transparentrecording medium even by using a semiconductor near-infrared laser withthe low output of approx. several tens of mW.

The typical composition for producing a recording layer of a transparentrecording medium according to the present invention comprises 3-30 partsof a developer, 3-30 parts of an organic acid metal salt or leuco dye,3-30 parts of a binder and 0.001-1 parts of a near-infrared absorbingmaterial. A solution of these components dissolved in a solvent tocontain 10-30% of solid portions is applied to a transparent supportingmember and dried, so that a transparent recording medium can beobtained. In addition, recording layers may be provided on both sides ofthe supporting member if necessary. The transparent recording mediumaccording to the present invention prepared in this manner is of use asa masking material for print platemaking, an OHP film, a slide film,duplicating draft or a photomask for manufacturing the circuit patternof a resin wiring board or integrated circuit.

Recently, the direct platemaking method has been developed for directlymaking a printing plate outputting an image or character designed on acomputer without use of a draft film. Simplified steps for printing haveenabled the time required for printing to be greatly shortened. However,in the field of general commercial printing, especially offset printing,the platemaking step using a draft film is employed in leading methods,in which a silver salt photography film is employed as a maskingmaterial for platemaking. The silver salt photography method, thoughgood in image quality, has problems such as disposal of developmentalprocess liquid, and therefore alternative materials to silver saltphotograph are sought for. Because of being free from theabove-mentioned problems, a transparent recording medium is useful as analternative to silver salt photography film. The present inventivemethod for making a plate by using a transparent recording medium inprinting an image onto a presensitized aluminum plate (PS plate) foroffset printing is almost the same as the conventional method for makinga plate by using a silver salt photographic film. After superimposing atransparent recording medium according to the present invention on a PSplate, an image is exposed by irradiating a light source such as atungsten lamp, halogen lamp, xenon lamp and mercury lamp from the sideof the transparent recording medium, so that a plate for offset printingcan be obtained.

A new indoaniline metal complex according to the present invention isuseful also as a near-infrared absorbing material, especially as anelement for efficiently converting near-infrared laser rays into heatused in an optical recording medium such as optical disk. With anelevating molar extinction coefficient of an indoaniline metal complex,the efficiency of converting near-infrared laser rays into heatincreases, so that an image with a sufficiently high recording densitycan be obtained on a transparent recording medium in a small consumedamount by using even low-output near-infrared laser rays. With the newindoaniline metal complexes according to the present invention, themaximum wavelength of absorption shifts to longer wavelengths, the molarextinction coefficient also rises sharply and the efficiency ofconverting near-infrared laser rays into heat is greatly improved ascompared with a metal-contained indoaniline-type compounds described inJapanese Patent Laid-Open (ko-kai) 227569/1988.

An optical recording medium manufactured by using a new indoanilinemetal complex according to the present invention comprises materialssimilar to those of a transparent recording medium. A substrate, binder,singlet oxygen quencher, other series of mixible coloring substances andthe like are used in common. Film forming can be executed by a generalfilm-forming technique such as vacuum evaporation, sputtering, doctorblade, cast, spinner or soaking.

In addition to a transparent recording medium, masking material forprint platemaking, optical recording medium, new indoaniline metalcomplexes represented by the general formula (1) or (2) serve also asgreen-type coloring substance, coloring substance for heat-sensitivetranscription, coloring substance for ink-jet printers, heat rayshielding agents, safety filters for sensitive materials, cut filtersfor semiconductor elements, color filters, liquid crystals, antihalationmaterial for sensitive materials, optical cards, photopolymerizationinitiators, physiological activating substances and medicaments. Inaddition, reaction intermediates, new indoaniline metal complexesrepresented by the general formula (3) or (4) serve also as blue-typecoloring substance, green-type coloring substance, coloring substancefor heat-sensitive transcription, coloring substance for ink-jetprinter, heat rays shielding agent, safety filters for sensitivematerials, cut filters for semiconductor elements, color filters, liquidcrystals, antihalation material for sensitive materials, optical cards,photopolymerization initiators, physiological activating substances andmedicaments. In addition, reaction intermediates,4-hydroxyphenanthoridine compounds represented by the general formula(6) and 4-hydroxyacridine derivatives represented by the general formula(7) are not only used as raw materials of dyes or pigments but also areutilized as physiological activating substances and medicaments.

EXAMPLES

Hereinafter, the present invention will be described in detail byreferring to prepared examples and examples of compounds according tothe present invention but is not restricted by these prepared examplesand examples.

Example 1

Preparation of indoaniline metal complexes with the phenanthridineskeleton

Prepared Example 1-1

Preparation of the indoaniline metal complex described in theexemplified compound 1-1

Synthesis was carried out in accordance with the following reactionscheme. ##STR17## 1-1-1! Synthesis ofN-(2-chlorobenzylidene)-2'-hydoroxyaniline (12)

A mixed solution comprising 12.00 g of o-aminophenol (10), 14.06 g of2-chlorobenzaldehyde (11) and 100 ml of ethanol was allowed to react at75° C. for a period of 5 hr. After the completion of the reaction, theethanol was distilled away. After purifying the residue by columnchromatography, 22.19 g of yellow crystal ofN-(2-chlorobenzylidene)-2'-hydroxyaniline (12) was obtained onrecrystallization by hexane-chloroform (yield 95.8%).

Analytical data

m.p.=94.0 (°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 9.14(s,1H), 8.20(dd, 1H, J=7.2, 2.1Hz),7.44-7.32 (m, 4H), 7.23 (dd, 1H, J=7.0, 1.4 Hz) 7.19 (d, 1H, J=1.2 Hz),7.02(d, 1H, J=7.8 Hz), 6.92(t, 1H, J=7.5 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 153.4, 152.6, 136.2, 135.4, 132.9,132.3, 130.1, 129.5, 128.3, 127.1, 120.2, 116.2, 115.2

IR (cm⁻¹, KBr) 3420, 1616, 1597, 1582, 1561, 1484, 1438, 1372, 1271,1250, 1233, 1211, 1174, 1147, 1050, 1027, 964, 934, 879, 855, 795, 759,739, 699, 572, 517, 499, 472, 454

MS (FAB, NBA)

m/z =232 (M⁺ +1)

FIGS. 1 and 2 show spectral charts of ¹ H-NMR and ¹³ C-NMR.

1-1-2 ! Synthesis of 4-hydroxyphenanthridine (13)

After putting 4.3 g of metal potassium and 1 mg of iron nitrateenneahydrate into 150 ml of liquid ammonium, reaction was allowed toproceed at -35° C. for a period of one hour with 3.85 g ofN-(2-chlorobenzylidene)-2'-hydroxyaniline (12) added. After thecompletion of the reaction, ammonium was removed. After purifying theresidue by column chromatography, 1.02 g of pale yellow crystal of4-hydroxyphenanthridine (13) was obtained on recrystallization by ethylacetate (yield 31.5%).

Analytical data

m.p.=191.0 (°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 9.84(br, 1H), 9.32(s,1H), 8.75(d, 1H,J=8.3 Hz), 8.24(d, 1H, J=8.0 Hz), 8.18(d, 1H, J=8.0 Hz), 7.93(t, 1H,J=7.7 Hz), 7.79(t, 1H, J=7.6 Hz) 7.56(t, 1H, J=8.0 Hz), 7.16(d, 1H,J=8.0 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 154.0, 150.9, 133.5, 131.9, 131.4,128.9, 128.1, 127.8, 126.2, 124.5, 122.6, 112.7, 112.3

IR (cm⁻¹, KBr) 3313, 1615, 1581, 1526, 1492, 1470, 1442, 1410, 1349,1318, 1295, 1260, 1213, 1170, 1061, 893, 770, 752, 730, 658, 553

MS (FAB, NBA)

m/z=196 (M⁺ +1)

FIGS. 3 and 4 show spectral charts of ¹ H-NMR and ¹³ C-NMR,respectively.

1-1-3! Synthesis of the indoaniline (22) described in the exemplifiedcompound 3-1

A mixture comprising 390 mg of 4-hydroxyphenanthridine (13), 430 mg of2-amino-5-diethylaminotoluene hydrochloride (21) and 15 ml of ethanolwas stirred at 20° C. and a solution comprising 1.02 g of silver nitratedissolved in 4.5 ml of water was added thereto drop-by-drop. Then, 1.7ml of 25% ammonia solution was added and the reaction was allowed toproceed at 20° C. for a period of 24 hr. After the completion of thereaction, the reacted solution was introduced into water. Afterextraction by ethyl acetate, the extract was concentrated. Afterpurification by column chromatography, 259 mg of deep blue crystal ofindoaniline (22) was obtained on recrystallization by hexane-ethylacetate (yield 35.1%).

Analytical data

m.p.=182.5 (°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 10.07(d, 1H, J=8.7 Hz), 9.43(s,1H),8.06(d, 1H, J=6.1 Hz), 7.86(t, 1H, J=7.8 Hz), 7.75(t, 1H, J=7.2 Hz),7.55(d, 1H, J=10.2 Hz) 6.83(d, 1H, J=10.4 Hz), 6.74(br, 1H) 6.69(d, 1H,J=8.6 Hz) 6.59(br, 1H), 3.44(quartet, 4H, J=7.0 Hz), 2.48(s, 3H),1.24(t, 6H, J=7.0 Hz)

IR (cm⁻¹, KBr) 3423, 2964, 2923, 1654, 1597, 1525, 1500, 1458, 1394,1372, 1353, 1297, 1263, 1237, 1198, 1159, 1146, 1111, 1086, 1030, 997,922, 841, 812, 753, 669, 617

MS (FAB, NBA)

m/z =370 (M⁺ +1)

FIG. 5 shows a spectral chart of ¹ H-NMR. The visible to near-infraredabsorption spectrum (ethanol solution) had a maximum wavelength ofabsorption of 664 nm (molar extinction coefficient=22,000).

1-1-4! Synthesis of the indoaniline metal complex (24) described in theexemplified compound 1-1

With 5 ml of aqueous solution containing 210 mg of copper perchloratehexahydrate (23) added to 10 ml of ethanol solution containing 100.6 mgof indoaniline (22), reaction were allowed to proceed at 20° C. for aperiod of 2 hr. After the completion of the reaction, the precipitatedcrystals were taken out by filtration and washed with a small amount ofwater and ethanol, followed by 4-hr reduced-pressure drying to obtain136.4 mg of black crystal of indoaniline metal complexe (24) (yield100%).

Analytical data

m.p.=300(°C.) or higher.

IR (cm⁻¹, KBr) 3425, 1621, 1588, 1572, 1519, 1483, 1449, 1440, 1408,1382, 1327, 1279, 1242, 1193, 1172, 1146, 1089, 1011, 989, 922, 874,849, 829, 805, 758, 739, 674, 645, 612, 507, 455

FIG. 6 shows a spectral chart of IR. The visible to near-infraredabsorption spectrum (acetone solution) had a maximum wavelength ofabsorption 795 nm (molar extinction coefficient=163,000).

Prepared Example 1-2

Preparation of the indoaniline metal complex described in theexemplified compound 1-2

1-2-1! Synthesis of the indoaniline described in the exemplifiedcompound 3-2

While stirring a mixture comprising 207 mg of 4-hydroxyphenanthridine(13), 237 mg of N,N-diethyl-p -phenylenediamine and 6.8 ml of ethanol at20° C., a solution comprising 170 mg of silver nitrate dissolved in 0.75ml of water was added thereto drop-by-drop. Next, with 0.85 ml of 25%ammonia solution added to the mixture, reaction was allowed to proceedat 20° C. for a period of 1.5 hr. Furthermore, a solution comprising 340mg of silver nitrate dissolved in 1.5 ml of water was added theretodrop-by-drop and the mixed solution was allowed to react at 20° C. for aperiod of 3 hr. After the completion of the reaction, the reactedsolution was introduced into water. After extraction by chloroform, theextract was concentrated. After purification by silica gel columnchromatography, 129 mg of indoaniline described in the exemplifiedcompound 3-2 was obtained (yield 36.2%).

Analytical data

m.p.=176.7-178.2(° C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 9.98(d, 1H, J=8.6 Hz), 9.43(s, 1H),8.06(d, 1H, J=8.0 Hz), 7.87(ddd, 1H, J=8.6, 7.9, 1.2 Hz), 7.76(dd, 1H,J=8.0, 7.9 Hz), 7.59(d, 1H, J=10.2 Hz) 7.10(d, 2H, J=8.8 Hz), 6.84(d,1H, J=10.2 Hz) 6.82(d, 2H, J=8.8 Hz), 3.46(quartet, 2H, J=6.9 Hz),1.26(t, 3H, J=6.9 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 184.9, 155.4, 142.7, 133.0, 132.4,131.4, 130.7, 129.5, 129.1, 128.5, 127.6, 126.7, 125.3, 123.0, 119.4,112.0, 45.1, 12.6

IR (cm⁻¹, KBr) 2967, 1651, 1590, 1508, 1397, 1349, 1299, 1269, 1087,997, 851, 818, 795, 760

MS (FAB, NBA)

m/z =356 (M⁺ +1)

The visible to near-infrared absorption spectrum (acetone solution) hasa maximum wavelength of absorption 615.4 nm (molar extinctioncoefficient=16,500).

1-2-2! Preparation of the indoaniline metal complex described in theexemplified compound 1-2

With 1.87 ml of aqueous solution containing 93.4 mg of copperperchlorate hexahydrate (23) added to 3 ml of ethanol solutioncontaining 35.5 mg of indoaniline described in the exemplified compound3-2, reaction was allowed to proceed at 20° C. for a period of 5 hr.After the completion of the reaction, the precipitated crystals weretaken out by filtration and washed with a small amount of water andethanol, followed by 4-hr reduced-pressure drying to obtain 44.0 mg ofdeep green crystal of indoaniline metal complexe described in theexemplified compounds 1-2 (yield 90.3%).

Analytical data

m.p.=300(°C.) or higher

IR (cm⁻¹, KBr) 1573, 1425, 1382, 1330, 1277, 1245, 1136, 1072, 1014,823, 738, 618

The visible to near-infrared absorption spectrum (acetone solution) hasa maximum wavelength of absorption 791 nm (molar extinctioncoefficient=98,700).

Prepared Example 1-3

Preparation of the indoaniline metal complex described in theexemplified compound 1-7

1-3-1! Synthesis of the indoaniline described in the exemplifiedcompound 3-7

While stirring a mixture comprising 228 mg of 4-hydroxyphenanthridine(13), 224 mg of N,N-di-sec-butyl-p-phenylenediamine and 7.5 ml ofethanol at 20° C., a solution comprising 187 mg of silver nitratedissolved in 0.82 ml of water was added thereto drop-by-drop. Next, with0.94 ml of 25% ammonia solution added to the mixture, reaction wasallowed to proceed at 20° C. for a period of 2 hr. Furthermore, asolution comprising 375.5 mg of silver nitrate dissolved in 1.65 ml ofwater was added thereto drop-by-drop and reaction was allowed to proceedat 20° C. for a period of 12 hr. After the completion of the reaction,the reacted solution was introduced into water. After extraction bychloroform, the extract was concentrated. On purification by silica gelcolumn chromatography, 133 mg of indoaniline described in theexemplified compound 3-7 was obtained (yield 34.1%).

Analytical data

m.p.=86.8°-87.5(° C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 9.96(d, 1H, J=8.7 Hz), 9.44(s, 1H),8.07(d, 1H, J=9.4 Hz), 7.87(ddd, 1H, J=8.7, 6.7, 1.0 Hz), 7.76(dd, 1H,J=9.4, 6.7 Hz), 7.58(d, 1H, J=10.4 Hz), 7.02(d, 2H, J=8.6 Hz), 6.83(d,1H, J=10.4 Hz) 6.72(d, 2H, J=8.6 Hz), 3.56-3.44(m,1H), 1,70-1.29(m, 2H)1.25(d, 3H, J=6.3 Hz), 1.00(t, 3H, J=7.4 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 184.8, 155.5, 154.8, 147.3, 142.6,139.8, 132.9, 132.5, 131.3, 130.7, 130.4, 129.5, 129.1, 128.5, 126.7,125.0, 113.5, 50.3, 29.6, 20.2, 10.4

IR (cm⁻¹, KBr) 3368, 2979, 1637, 1605, 1590, 1477, 1422, 1339, 1269,1163, 1139, 1090, 996, 833, 814, 756

MS (FAB, NBA)

m/z =356 (M⁺ +1)

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 599 nm (molar extinctioncoefficient=11,220).

1-3-2! Preparation of the indoaniline metal complex described in theexemplified compound 1-7

With 1.87 ml of aqueous solution containing 78.4 mg of copperperchlorate hexahydrate (23) added to 3 ml of ethanol solutioncontaining 30.0 mg of indoaniline described in the exemplified compound3-7, reaction was allowed to proceed at 20° C. for a period of 2 hr.After the completion of the reaction, the precipitated crystals were astaken out by filtration and washed with a small amount of water andethanol, followed by 4-hr reduced-pressure drying to obtain 12.6 mg ofblack crystal of the indoaniline metal complex described in theexemplified compound 1-7 (yield 30.7%).

Analytical data

m.p.=300(°C.) or higher

IR (cm⁻¹, KBr) 3228, 3069, 1589, 1573, 1515, 1449, 1384, 1330, 1227,1246, 1169, 1139, 1104, 1016, 823, 740, 670, 618, 513, 456

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 774 nm (molar extinctioncoefficient=104,000).

Prepared Example 1-4

Preparation of the indoaniline metal complex described in theexemplified compound 1-10

1-4-1! Synthesis of N-acetyl-N',N'-di(2-ethylhexyl)-p-phenylenediamine

A mixed solution comprising 1.00 g of p-aminoacetanilide, 16.72 g of2-ethylhexylbromide, 4.59 g of sodium carbonate and 20 ml ofmethylcellosolve is allowed to react at 113° C. for a period of 24 hr.After the completion of the reaction, the reacted solution wasintroduced into water and the product was extracted by ethyl acetate.After ethyl acetate was distilled away, the residue was purified bysilica gel column chromatography, 1.17 g of oil ofN-acetyl-N',N'-di(2-ethylhexyl)-p-phenylenediamine was obtained (yield48.9%).

Analytical data

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 7.25(d, 2H, J=8.8 Hz), 7.07(s, 1H),6.60(d,2H, J=9.0 Hz), 3.21-3.12(m, 4H), 2.12(s, 3H), 1.76(br, 2H),1,40-1.20(m, 16H), 0.88(t, 6H, J=6.4 Hz), 0.86(t, 6H, J=7.2 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 168.1, 145.9, 126.1, 122.2, 113.1, 56.6,36.7, 30.7, 28.7, 24.2, 23.9, 23.2, 14.1, 10.7

IR (cm⁻¹, KBr) 3289, 2959, 2928, 2858, 1657, 1601, 1538, 1516, 1461,1417, 1369, 1322, 1269, 1227, 1186, 813, 516

MS (FAB, NBA)

m/z =375 (M⁺ +1)

1-4-2! Preparation of N,N-di(2-ethylhexyl)-p-phenylenediamine

A mixed solution comprising 8 ml of 30% sodium hydroxide solution, 1.012g of N-acetyl-N',N'-di(2-ethylhexyl)-p-phenylenediamine and 10 ml ofethanol was allowed to react at 75° C. for a period of 5 hr. After thecompletion of the reaction, the reacted solution was introduced intowater and the product was extracted by ethyl acetate. After ethylacetate was distilled away, the residue was purified by silica gelcolumn chromatography to obtain 501 mg of oil ofN,N-di(2-ethylhexyl)-p-phenylenediamine (yield 53.4%).

Analytical data

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 6.62(s, 4H), 3.55(br, 4H), 1,63(br, 2H)1.45-1.20(m, 16H), 0.88(t, 6H, J=6.4 Hz), 0.84(t, 6H, J=7.4 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 143.2, 137.0, 116.9, 116.7, 57.8, 36.9,30.8, 28.8, 24.0, 23.2, 14.1, 10.7

IR (cm⁻¹, KBr) 3446, 3355, 2958, 2928, 2871, 2858, 1681, 1599, 1557,1513, 1459, 1376, 1363, 1310, 1268, 1227, 1179, 1155, 1114, 1041, 938,818, 766, 727, 667, 512

MS (FAB, NBA)

m/z=333 (M⁺ +1)

1-4-3! Synthesis of the indoaniline described in the exemplifiedcompound 3-10

While stirring a mixture comprising 267 mg of 4-hydroxyphenanthridine(13), 430 mg of N,N-di(2-ethylhexyl)-p-phenylenediamine and 8 ml ofethanol at 20° C., a solution comprising 219 mg of silver nitratedissolved in 0.9 ml of water was added thereto drop-by-drop. 30 minlater, 1.1 ml of 25% ammonia solution was added to the mixture, furthera solution comprising 438 mg of silver nitrate dissolved in 1.7 ml ofwater was added thereto drop-by-drop and reaction was allowed to proceedat 20° C. for a period of 1.5 hr. After the completion of the reaction,the reacted solution was introduced into water. After extraction bychloroform, the extract was concentrated. On purification by silica gelcolumn chromatography, 141 mg of indoaniline described in theexemplified compound 3-10 was obtained (yield 20.8%).

Analytical data

m.p.=87.6°-88.0(°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 10.02(dd, 1H, J=8.8, 1.0 Hz), 9.41(d, 1H,J=0.6 Hz), 8.05(dd, 1H, J=8.0, 0.9 Hz), 7.86(ddd, 1H, J=8.8, 7.2, 1.6Hz), 7.75(ddd, 1H, J=8.0, 7.2, 1.0 Hz), 7.65(d, 1H, J=10.3 Hz), 7.10(d,2H, J=9.0 Hz), 6.85(d, 1H, J=10.3 Hz), 6.78(d, 2H, J=9.0 Hz),3.36-3.29(m,4H), 1.88-1.83(m, 2H) 1.45-1.23(m, 16H), 0.98-0.90(m, 12H)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 185.0, 155.2, 153.8, 148.1, 142.6,138.3, 133.0, 132.3, 131.5, 130.3, 129.6, 129.0, 128.4, 126.7, 125.5,112.8, 56.5, 37.1, 30.7, 28.7, 24.0, 23.2, 14.1, 10.7

IR (cm⁻¹, KBr) 2957, 2926, 2870, 1643, 1590, 1507, 1364, 1295, 1232,1180, 1139, 1084, 815

MS (FAB, NBA)

m/z=525 (M⁺ +1)

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 622.6 nm (molar extinctioncoefficient=16,760).

1-4-4! Preparation of the indoaniline metal complex described in theexemplified compound 1-10

With 1.9 ml of aqueous solution containing 89.1 mg of copper perchloratehexahydrate (23) added to 4.3 ml of ethanol solution containing 50.0 mgof indoaniline described in the exemplified compound 3-10, reaction wasallowed to proceed at 20° C. for a period of 6 hr. After the completionof the reaction, the precipitated crystals were taken out by filtrationand washed with a small amount of water and ethanol, followed by 4-hrreduced-pressure drying to obtain 57.0 mg of green crystal of theindoaniline metal complex described in the exemplified compound 1-15(yield 91.2%).

Analytical data

m.p.=300(°C.) or higher

IR (cm⁻¹, KBr) 2956, 2927, 1575, 1392, 1350, 1134, 1095, 1016, 826, 736,622

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 809.4 nm (molar extinctioncoefficient=151,500).

Prepared Examples 1-5

Preparation of the indoaniline metal complex described in theexemplified compound 1-11

1-5-1! Synthesis of N-acetyl-N',N'-dihexadecyl-p-phenylenediamine

A mixed solution comprising 1.00 g of p-aminoacetanilide, 20.34 g ofhexadecylbromide, 3.53 g of sodium carbonate and 20 ml ofmethylcellosolve is allowed to react at 113° C. for a period of 9 hr.After the completion of the reaction, the reacted solution wasintroduced into water and the product was extracted by ethyl acetate.After ethyl acetate was distilled away, the residue was purified bysilica gel column chromatography, 3.95 g ofN-acetyl-N',N'-dihexadecyl-p-phenylenediamine crystal was obtained onrecrystallization by dichloromethane (yield 99.0%).

Analytical data

m.p=56.3°-57.3(°C.).

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 7.25(d, 2H, J=8.7 Hz), 7.05(s, 1H),6.57(d, 2H, J=8.9 Hz), 3.21(t, 4H, J=7.6 Hz), 2.12(s, 3H) 1.54(br, 4H)1.26(br, 52H), 0.88(t, 6H, J=6.6 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 168.1, 145.7, 126.1, 122.6, 112.0, 51.3,31.9, 29.7, 29.4, 27.2, 24.2, 22.7, 14.1

IR (cm⁻¹, KBr) 3278, 2920, 2851, 1654, 1555, 1541, 1514, 1468, 1363,1318

MS (FAB, NBA)

m/z=599 (M⁺ +1)

1-5-2! Synthesis of N,N-dihexadecyl-p-phenylenediamine

A mixed solution comprising 5 ml of 30% sodium hydroxide solution, 3.257g of N-acetyl-N',N'-dihexadecyl-p-phenylenediamine and 10 ml of ethanolwas allowed to react at 75° C. for a period of 9 hr. After thecompletion of the reaction, the reacted solution was introduced intowater and the product was extracted by ethyl acetate. After ethylacetate was distilled away, the residue was purified by silica gelcolumn chromatography and 2.138 g of N,N-dihexyadecyl-p-phenylenediaminecrystal was obtained on recrystallization by dichloromethane (yield70.6%).

Analytical data

m.p =43.0°-44.0 (°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 6.64(d, 2H, J=8.9 Hz), 6.58(d, 2H, J=9.0H), 3.11(t, 4H, J=7.5H), 1.49(br, 4H), 1.26(br, 52H) 0.88(t, 6H, J=6.7Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 142.5, 136.8, 116.9, 115.5, 52.3, 32.0,29.7, 29.4, 27.3, 22.7, 14.1

IR (cm⁻¹, KBr) 3433, 3207, 2919, 2851, 1637, 1612, 1512, 1467, 1363,1275, 1089, 830, 722

MS (FAB, NBA)

m/z=557 (M⁺ +1)

1-5-3! Synthesis of the indoaniline described in the exemplifiedcompound 3-11

While stirring a mixture comprising 207 mg of 4-hydroxyphenanthridine(13), 557 mg of N,N-dihexadecyl-p-phenylenediamine and 6.8 ml of ethanolat 20° C., a solution comprising 170 mg of silver nitrate dissolved in0.8 ml of water was added thereto drop-by-drop. 45 min later, 0.9 ml of25% ammonia solution was added to the mixture, further a solutioncomprising 340 mg of silver nitrate dissolved in 1.5 ml of water wasadded thereto drop-by-drop and reaction was allowed to proceed at 20° C.for a period of 8 hr. After the completion of the reaction, the reactedsolution was introduced into water. After extraction by chloroform, theextract was concentrated. On purification by silica gel columnchromatography, 99.3 mg of indoaniline described in the exemplifiedcompound 3-11 was obtained (yield 13.3%).

Analytical data

m.p.=66.3 (°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 10.02(d, 1H, J=8.7 Hz), 9.43(s, 1H),8.07(d, 1H, J=8.0 Hz), 7.87(dd, 1H, J=7.3, 7.3 Hz), 7.76(dd, 1H, J=7.7,7.0 Hz), 7.63(d, 1H, J=10.4 Hz), 7.10(d, 2H, J=8.9 Hz), 6.84(d, 1H,J=10.4 Hz), 6.74(d, 2H, J=8.9 Hz), 3.35(t, 4H, J=7.3 Hz), 1.65(m, 4H),1.36-1.26(m, 52H), 0.88(t, 6H, J=6.2 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 185.0, 155.3, 153.9, 148.0, 142.6,138.3, 134.2, 133.0, 132.4, 131.5, 130.4, 129.6, 129.0, 128.5, 126.8,125.7, 118.9, 51.3, 32.0, 29.73, 29.71, 29.66, 29.57, 29.50, 29.46,29.39, 27.43, 27.2, 22.7, 14.1

IR (cm⁻¹, KBr) 2919, 2850, 1650, 1591, 1508, 1465, 1398, 1372, 1305,1093, 819

MS (FAB, NBA)

m/z=749 (M⁺ +1)

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 623.4 nm (molar extinctioncoefficient=17,200).

1-5-4! Preparation of the indoaniline metal complex described in theexemplified compound 1-11

With 1.5 ml of aqueous solution containing 80.6 mg of copper perchloratehexahydrate (23) added to 7 ml of ethanol solution containing 65.1 mg ofindoaniline described in the exemplified compound 3-11, reaction wasallowed to proceed at 20° C. for a period of 12 hr. After the completionof the reaction, the precipitated crystals were taken out by filtrationand washed with a small amount of water and ethanol, followed by 4-hrreduced-pressure drying to obtain 57.5 mg of green crystal ofindoaniline metal complexe described in the exemplified compound 1-11(yield 37.6%).

Analytical data

m.p.=213°-215 (°C.)

IR (cm⁻¹, KBr) 2920, 2850, 1574, 1383, 1338, 1134, 1104, 1016, 825, 741,617

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 789.8 nm (molar extinctioncoefficient=87,940).

Prepared Example 1-6

Preparation of the indoaniline metal complex described in theexemplified compound 1-15

1-6-1! Synthesis ofN-acetyl-N',N'-di(2-(2-methoxy)ethoxy)ethyl-p-phenylenediamine

A mixed solution comprising 1.00 g of P-aminoacetanilide, 10.00 g of2-chloro-2-methoxydiethyl ether, and 5.00 g of sodium carbonate isallowed to react at 150° C. for a period of 12 hr. After the completionof the reaction, the reacted solution was washed by water and purifiedby column chromatography, so that 1.90 g of oil ofN-acetyl-N',N'-di(2-(2-methoxy)ethoxy)-ethyl-p-phenylenediamine (yield80.3%).

Analytical data

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 7.44(s, 1H), 7.27(d, 2H, J=9.0 Hz),6.64(d, 2H, J=8.9H), 3.65-3.50(m, 16H), 2.11(s, 3H)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 168.3, 145.0, 127.1, 122.4, 111.9, 71.9,70.5, 68.4, 59.0, 51.0, 24.1

IR (cm⁻¹, KBr) 3479, 3301, 3182, 3114, 3064, 2878, 1655, 1600, 1519,1455, 1418, 1369, 1324, 1268, 1228, 1195, 1112, 1023, 928, 846, 817,666, 603, 522

MS (FAB, NBA)

m/z=355 (M⁺ +1)

1-6-2! Preparation ofN,N-di(2-(2-methoxy)ethoxy)ethyl-p-phenylenediamine

A mixed solution comprising 25 ml of 30% sodium hydroxide solution,1.795 g of N-acetyl-N',N'-di(2-(2-methoxy)ethoxy)ethyl-p-phenylenediamine and 20 ml of ethanol was allowed to react at75° C. for a period of 10 hr. After the completion of the reaction, thereacted solution was introduced into water and the product was extractedby ethyl acetate. After ethyl acetate was distilled away, the residuewas purified by silica gel column chromatography to obtain 1.281 g ofoil of N, N-di(2-(2-methoxy)ethoxy)ethyl-p-phenylenediamine (yield81.0%).

Analytical data

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 6.62(s, 4H), 3.67-3.28(m, 24H)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 141.1, 137.2, 116.6, 114.5, 71.7, 70.2,68.5, 58.8, 51.6

IR (cm⁻¹, KBr) 3427, 3350, 2876, 1650, 1635, 1558, 1517, 1472, 1456,1360, 1274, 1197, 1108, 1027, 976, 814, 667, 517

MS (FAB, NBA)

m/z=313 (M⁺ +1)

1-6-3! Synthesis of the indoaniline described in the exemplifiedcompound 3-15

While stirring a mixture comprising 145 mg of 4-hydroxyphenanthridine(13), 219 mg of N,N-di(2-(2-methoxy)ethoxy)ethyl-p-phenylenediamine and4.3 ml of ethanol at 20° C., a solution comprising 119 mg of silvernitrate dissolved in 0.5 ml of water was added thereto drop-by-drop. 30min later, 0.6 ml of 25% ammonia solution was added to the mixture,further a solution comprising 238 mg of silver nitrate dissolved in 1.0ml of water was added thereto drop-by-drop and reaction was allowed toproceed at 20° C. for a period of 1.5 hr. After the completion of thereaction, the reacted solution was introduced into water. Afterextraction by chloroform, the extract was concentrated. On purificationby silica gel column chromatography, 194 mg of indoaniline described inthe exemplified compound 3-15 was obtained (yield 54.9%).

Analytical data

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 9.98(d, 1H, J=8.7 Hz), 9.43(s, 1H),8.07(d, 1H, J=8.0 Hz), 7.88(dd, 1H, J=8.7, 7.6 Hz), 7.78(dd, 1H, J=7.6,7.0 Hz), 7.59(d, 1H, J=10.3 Hz), 7.06(d, 2H, J=8.7 Hz), 6.84(d, 2H,J=8.7 Hz), 6.835(d, 1H, J=8.7 Hz), 3.70(m, 8H), 3.65(m, 4H), 3.56(m,4H), 3.40(s, 6H)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 185.0, 155.4, 154.7, 147.5, 142.6,139.0, 132.9, 132.5, 131.4, 130.7, 130.3, 129.4, 129.1, 128.5, 126.7,125.0, 112.1, 72.0, 70.7, 68.5, 59.1, 51.2

IR (cm⁻¹, KBr) 2878, 1651, 1591, 1508, 1393, 1353, 1240, 1138, 997, 817

MS (FAB, NBA)

m/z=504 (M⁺ +1)

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 605.6 nm (molar extinctioncoefficient=11,700).

1-6-4! Preparation of the indoaniline metal complex described in theexemplified compound 1-15

With 2 ml of aqueous solution containing 147.0 mg of copper perchloratehexahydrate (23) added to 6 ml of ethanol solution containing 79.3 mg ofindoaniline described in the exemplified compound 3-15, reaction wasallowed to proceed at 20° C. for a period of 12 hr. After the completionof the reaction, the deposited crystals were taken out by filtration andwashed with a small amount of water and ethanol, followed by 4-hrreduced-pressure drying to obtain 39.8 mg of brown crystals of theindoaniline metal complex described in the exemplified compound 1-15(yield 20.0%).

Analytical data

m.p.=300(°C.) or higher

IR (cm⁻¹, KBr) 1574, 1537, 1377, 1332, 1122, 1096, 1013, 824, 736, 622

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 798.2 nm (molar extinctioncoefficient=110,200).

Prepared Examples 1-7

Preparation of the indoaniline metal complex described in theexemplified compound 1-25

1-7-1! Synthesis of the indoaniline described in the exemplifiedcompound 3-25

While stirring a mixture comprising 207 mg of 4-hydroxyphenanthridine(13), 221 mg of p-aminodiphenylamine hydrochloride and 6.8 ml of ethanolat 20° C., a solution comprising 170 mg of silver nitrate dissolved in0.8 ml of water was added thereto drop-by-drop. 30 min later, with 0.9ml of 25% ammonia solution having being added and moreover a solutioncomprising 340 mg of silver nitrate dissolved in 1.5 ml of water beingdropwise added to the mixed solution, reaction was allowed to proceed at20° C. for a period of 6 hr. After the completion of the reaction, thereacted solution was introduced into water. After extraction bychloroform, the extract was concentrated. On purification by silica gelcolumn chromatography, 129 mg of indoaniline described in theexemplified compound 3-25 was obtained (yield 34.4%).

Analytical data

m.p.=198.2-199.7(°C.)

¹ H-NMR (ppm, ref -TMS, CDCl₃) 9.92(d, 1H, J=8.6 Hz), 9.46(s, 1H),8.08(d, 1H, J=7.7 Hz), 7.91(dd, 1H, J=8.6, 7.0 Hz), 7.79(dd, 1H, J=7.7,7.0 Hz), 7.54(d, 1H, J=10.3 Hz), 7.35-7.30(m, 2H), 7.27(s, 1H),7.21-7.04(m, 4H), 7.09-6.95(m, 3H), 6.85(d, 1H, J=10.3 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 184.9, 156.6, 155.9, 142.7, 142.4,142.4, 142.1, 132.8, 132.8, 131.6, 131.3, 130.4, 129.5, 129.3, 129.2,128.6, 126.4, 123.4, 121.9, 118.6, 117.5

IR (cm⁻¹, KBr) 3281, 1642, 1578, 1510, 1492, 1458, 1412, 1309, 1234,1162, 1137, 1091, 995, 841, 818, 805, 747, 693

MS (FAB, NBA)

m/z=376 (M⁺ +1)

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 576 nm (molar extinctioncoefficient=10,160).

1-7-2! Preparation of the indoaniline metal complex described in theexemplified compound 1-25

With 2 ml of aqueous solution containing 93.4 mg of copper perchloridehexahydrate (23) added to 3 ml of ethanol solution containing 37.5 mg ofindoaniline described in the exemplified compound 3-25, reaction wasallowed to proceed at 20° C. for a period of 12 hr. After the completionof the reaction, the precipitated crystals were taken out by filtrationand washed with a small amount of water and ethanol, followed by 4-hrreduced-pressure drying to obtain 45.3 mg of black crystal of theindoaniline metal complex described in the exemplified compound 1-25(yield 89.3%).

Analytical data

m.p.=300(°C.) or higher

IR (cm⁻¹, KBr) 1574, 1389, 1319, 1124, 1099, 1014, 824, 740

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 784 nm (molar extinctioncoefficient=62,700).

Prepared Example 1-8

Preparation of the indoaniline metal complex described in theexemplified compound 1-53

1-8-1! Synthesis of laur-5-chloro-2-nitroanilide

After, while cooled with ice, 20 ml of benzene solution containing 7.65g of n-lauroyl chloride was dropwise added to a mixed solutioncomprising 3.45 g of 5-chloro-2-nitroaniline, 1.29 g ofN,N-dimethylaminopyridine, 1.58 g of pyridine and 20 ml of benzene,reaction was allowed to proceed at room temperatures for a period of 8.5hr. After the completion of the reaction, the reacted solution is washedwith 0.1N hydrochloric acid and the solution was distilled away. Onrecrystallization of the precipitated crystals from hexane-ethylacetate, 4.75 g of laur-5-chloro-2-nitroanilide crystal was obtained(yield 67.0%).

Analytic data

m.p.=66.2 (°C.)

¹ H-NMR (ppm, ref-TMS, CDCl₃) 10.46(s, 1H), 8.94(d, 1H, J=2.5 Hz),8.17(d, 1H, J=9.4 Hz), 7.13(dd, 1H, J=9.4, 2.5 Hz), 2.50(t, 2H, J=7.5Hz), 1.75(m, 2 Hz), 1.43-1.26(m, 16H), 0.88(t, 3H, J=6.3 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 172.4, 142.8, 136.0, 134.2, 126.9,123.3, 121.7, 38.7, 31.9, 29.6, 29.4, 29.32, 29.30, 29.1, 25.2, 22.7,14.1

IR (cm⁻¹, KBr) 3332, 2917, 2850, 1683, 1609, 1578, 1502, 1330, 1258,1170, 919, 848

MS (FAB, NBA)

m/z=355 (M⁺ +1)

1-8-2! Synthesis of laur-5-dibutylamino-2-nitroanilide

A mixed solution of 2.13 g of laur-5-chloro-2-nitroanilide, 1.29 g ofdibutylamine, 0.33 g of potassium carbonate, 0.24 g of copper powder and3.6 mg of iodine was allowed to react at a reaction temperature of 155°C. for a period of 6 hr. After filtering the inorganic compounds outfrom the reacted solution, the filtered solution was purified by silicagel chromathography to obtain 1.47 g of yellow crystal oflaur-5-dibutylamino-2-nitroanilide (yield 54.5%).

Analytical data

m.p.=90.3 (°C.)

¹ H-NMR (ppm, ref-TMS, CDCl₃) 11.18(s, 1H), 8.19(d, 1H, J=2.7 Hz),8.12(d, 1H, J=9.7 Hz), 6.31(dd, 1H, J=9.7, 2.7 Hz), 3.39(t, 4H, J=7.7Hz), 2.47(t, 2H, J=7.5 Hz), 1.78-1.71(m, 2H), 1.68-1.58(m, 4H),1.46-1.26(m, 20H), 0.98(t, 6H, J=7.3 Hz), 0.88(t, 3H, J=6.0 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 172.9, 153.9, 138.3, 128.8, 124.5,106.2, 100.6, 51.2, 39.2, 31.9, 29.6, 29.44, 29.36, 29.31, 29.1, 25.5,22.7, 20.2, 14.1, 13.9

IR (cm⁻¹, KBr) 2918, 2850, 1610, 1569, 1275, 1219, 1178, 1091, 850, 741

MS (FAB, NBA)

m/z=448 (M⁺ +1)

1-8-3! Synthesis of laur-5-dibutylamino-2-aminoanilide

30 mg of 5% palladium carbon was added to 100 ml of ethanol solutioncontaining 330 mg of laur-5-dibutylamino-2-nitroanilide and thehydrogenation reaction was allowed to proceed at 40° C. for a period of7 hr. After the completion of the reaction, 5% palladium carbon isfiltered and ethanol was distilled away. On recrystallization of theprecipitated crystals by hexane-ethyl acetate, 215 mg oflaur-5-dibutylamino-2-aminoanilide (yield 69.8%).

Analytical data

m.p.=69.9°-71.6 (°C.)

¹ H-NMR (ppm, ref-TMS, CDCl₃) 7.57(br, 1H), 6.94(br, 1H), 6.71(br, 1H),6.41(br, 1H), 3.15(br, 4H), 2.35(t, 2H, J=7.4 Hz), 1.72(m, 2H), 1.50(m,4H), 1.48-1.26(m, 20H), 0.95-0.86(m, 9

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 171.6, 143.9, 128.2, 127.8, 121.1,111.3, 108.6, 51.6, 37.5, 31.9, 29.7, 29.6, 29.5, 29.4, 29.3, 25.9,22.7, 20.4, 14.1, 14.0

IR (cm⁻¹, KBr) 3288, 2915, 2850, 1650, 1516, 1468, 1424, 1370, 798, 718

MS (FAB, NBA)

m/z=417 (M⁺ +1)

1-8-4! Synthesis of the indoaniline described in the exemplifiedcompound 3-53

While stirring a mixed solution comprising 310.7 mg of4-hydroxyphenanthridine (13), 626.5 mg oflaur-5-dibutylamino-2-aminoanilide and 10 ml of ethanol at 20° C., asolution comprising 255.0 mg of silver nitrate dissolved in 1.0 ml ofwater was added thereto drop-by-drop. 30 min later, 1.28 ml of 25%ammonia solution was added, further a solution comprising 510.0 mg ofsilver nitrate dissolved in 2.0 ml of water was added theretodrop-by-drop and reaction was allowed to proceed at 20° C. for a periodof 1.5 hr. After the completion of the reaction, the reacted solutionwas introduced into water. After extraction by chloroform, the extractwas concentrated. On purification by silica gel column chromatography,55.2 mg of indoaniline described in the exemplified compound 3-53 wasobtained (yield 6.04%).

Analytical data

m.p.=67.7°-69.8(°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 9.66(d, 1H, J=8.3 Hz), 9.37(s, 1H),8.72(s, 1H), 8.19(d, 1H, J=2.0 Hz), 8.07(d, 1H, J=7.9 Hz), 7.81-7.76(m,2H), 7.72(d, 1H, J=10.3 Hz), 7.00(d, 1H, J=9.0 Hz), 6.86(dd, 1H, J=10.3,0.8 Hz), 6.46(dd, 1H, J=9.0, 2.0 Hz), 3.43(t, 4H, J=7.3 Hz), 2.35(t, 2H,J=7.5 Hz), 1.71-1.64(m, 6H) 1.47-1.40(m, 4H), 1.28-1.19(m, 16H), 1.01(t,6H, J=7.2 Hz), 0.87(t, 3H, J=5.8 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 183.9, 171.6, 154.7, 150.7, 150.5,142.3, 138.0, 133.0, 131.9, 131.3, 130.3, 130.1, 128.8, 127.4, 126.3,123.5, 107.1, 102.3, 51.2, 38.5, 31.8, 29.7, 29.5, 29.4, 29.30, 29.25,29.20, 29.19, 25.6, 22.6, 20.3, 14.1, 13.9

IR (cm⁻¹, KBr) 3356, 2922, 2852, 1608, 1588, 1462, 1361, 1227, 1089,1000, 803, 747

MS (FAB, NBA) m/z=610 (M⁺ +1)

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 659.2nm (molar extinctioncoefficient=26,700). 1-8-5! Preparation of the indoaniline metal complexdescribed in the exemplified compound 1-53

With 1 ml of aqueous solution containing 49.4 mg of copper perchloratehexahydrate (23) added to 4 ml of ethanol solution containing 32.2 mg ofindoaniline described in the exemplified compound 3-53, reaction wasallowed to proceed at 20° C. for a period of 15 hr. After the completionof the reaction, the precipitated crystals were taken out by filtrationand washed with a small amount of water and ethanol, followed by 4-hrreduced-pressure drying to obtain 34.9 mg of deep green crystals of theindoaniline metal complex described in the exemplified compound 1-53(yield 89.3%).

Analytical data

m.p.=300(°C.) or higher

IR (cm⁻¹, KBr) 2923, 2852, 1575, 1503, 1451, 1332, 1143, 1086, 814, 617

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 779nm (molar extinctioncoefficient=78,600).

Prepared Example 1-9

Preparation of the indoaniline metal complex described in theexemplified compound 1-57

With 5 ml of aqueous solution containing 52.4 mg of nickel perchloratehexahydrate added to 5 ml of ethanol solution containing 30.0 mg ofindoaniline described in the exemplified compound 3-10, reaction wasallowed to proceed at 20° C. for a period of 12 hr. After the completionof the reaction, the precipitated crystals were taken out by filtrationand washed with a small amount of water and ethanol, followed by 4-hrreduced-pressure drying to obtain 19.0 mg of green crystals of theindoaniline metal complex described in the exemplified compound 1-57(yield 50.8%).

Analytical data

m.p.=194°-197 (°C.)

IR (cm⁻¹, KBr) 3956, 2928, 2978, 1578, 1541, 1457, 1424, 1392, 1351,1169, 1130, 1098, 1012, 825, 740, 443

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 798.8 nm (molar extinctioncoefficient=100,800).

Prepared Example 1-10

Preparation of the indoaniline metal complex described in theexemplified compound 1-58

With 5 ml of aqueous solution containing 75.0 mg of iron perchloratehydrated added to 5 ml of ethanol solution containing 30.0 mg ofindoaniline described in the exemplified compound 3-10, reaction wasallowed to proceed at 20° C. for a period of 12 hr. After the completionof the reaction, the precipitated crystals were taken out by filtrationand washed with a small amount of water and ethanol, followed by 4-hrreduced-pressure drying to obtain 25.3 mg of deep green crystals of theindoaniline metal complex described in the exemplified compound 1-58(yield 67.8%).

Analytical data

m.p.=300 (°C.) or higher

IR (cm⁻¹, KBr) 2956, 2928, 2870, 1573, 1518, 1423, 1391, 1326, 1279,1243, 1139, 1095, 1014, 821, 613, 487, 447

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 811.2 nm (molar extinctioncoefficient=67,000).

Prepared Example 1-1

Preparation of the indoaniline metal complex described in theexemplified compound 1-131

1-11-1! Synthesis of N-(2-chloro-4-fluorobenzylidene)-2'-methoxyaniline

A mixed solution comprising 627.0 mg of o-anisidine, 807.1 mg of2-chloro-4-fluorobenzaldehyde and 50 ml of ethanol was allowed to reactfor a period of 24 hr at reflux temperature. After the completion of thereaction, 1.312 g of N-(2-chloro-4-fluorobenzylidene)-2'-methoxyanilinewas obtained as yellow oil on removal of ethanol (yield 97.8%).

Analytical data

IR (cm⁻¹, KBr) 3067,2932, 2829, 1600,1494, 1462, 1396, 1368, 1248, 1204,1180, 1204, 1114, 1041, 1028, 909, 859, 821, 747, 586, 488, 426

MS (FAB, NBA)

m/z=264 (M⁺ +1)

1-11-2! Preparation of 4-methoxy-6-fluorophenanthridine

After putting 1.05 g of metal potassium and 1 mg of iron nitrateenneahydrate into 70 ml of ammonia liquor, reaction was allowed toproceed at -60° C. for a period of one hour with 871.0 mg ofN-(2-chloro-4-fluorobenzylidene)-2'-methoxyaniline added. After thecompletion of the reaction, ammonia was removed. After purifying theresidue by column chromatography, 145.8 mg of4-methoxy-6-fluorophenanthridine was obtained as light brown crystals onrecrystallization from hexane-chloroform (yield 19.4%).

Analytical data

Sublimated at 145° C.

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 9.23(s,1H), 8.10(dd, 1H, J=10.5, 2.2 Hz),8.03(dd, 1H, J=8.8, 5.8 Hz), 7.95(d, 1H, J=8.1 Hz), 7.57(t, 1H, J=8.1Hz), 7.40(td, 1H, J=8.5, 2.3 Hz), 7.15(d, 1H, J=8.0 Hz), 4.11(s, 3H)

13C-NMR (ppm, ref.-TMS, CDCl₃) 163.9(d, J=249.3 Hz), 155.9, 151.1,135.3, 134.4(d, J=9.5 Hz), 131.3(d, 1H, J=9.6 Hz), 127.3, 124.6(d, J=4.1Hz), 123.4, 116.9(d, J=24.2 Hz), 114.0, 108.7, 107.4(d, J=22.3 Hz), 56.0

IR (cm⁻¹, KBr) 3425, 2934, 1623, 1504, 1469, 1254, 1156, 1118, 1028,840, 751

MS (FAB, NBA)

m/z=228 (M⁺ +1)

1-11-3! Preparation of 4-hydroxy-6-fluorophenanthridine

A mixed solution comprising 115 mg of 4-methoxy-6-fluorophenanthridineand 5 ml of 48% hydrobromic acid was allowed to react at 116° C. for aperiod of 14 hr. After the completion of the reaction, the reactedsolution was introduced into an aqueous solution of sodium carbonate andthe product was extracted by ethyl acetate. After ethyl acetate wasdistilled away, the residue was purified by column chromatography toobtain 104.5 mg of 4-hydroxy-6-fluorophenanthridine on recrystallizationfrom hexane (yield 96.9%).

Analytical data

Sublimated at 180° C.

¹ H-NMR (ppm, ref.-TMS, d₆ -DMSO) 9.89(s, 1H), 9.30(s, 1H), 8.57(dd, 1H,J=10.4, 0.9 Hz), 8.34(dd, 1H, J=8.6, 6.1 Hz), 8.16(d, 1H, J=8.2 Hz),7.67(td, 1H, J=8.6, 1.5 Hz), 7.55(t, 1H, J=8.0 Hz), 7.18(d, 1H, J=7.6Hz)

¹³ C-NMR (ppm, ref.-TMS, d₆ -DMSO) 163.6(d, J=246.8 Hz), 154.0, 150.2,134.3(d, J=9.5 Hz), 133.6, 132.2(d, J=9.9 Hz), 128.1, 124.1(d, J=3.8Hz), 123.4, 117.0(d, J=24.2 Hz), 113.2, 112.9, 107.9(d, J=22.6 Hz)

IR (cm⁻¹, KBr) 3328, 1622, 1584, 1526, 1473, 1422, 1411, 1315, 1288,1251, 1213, 1165, 1129, 1060, 895, 872, 833, 755, 705, 633, 547

MS (FAB, NBA)

m/z=214 (M⁺ +1)

1-11-4! Preparation of the indoaniline described in the exemplifiedcompound 3-131

While stirring a mixture comprising 59 mg of4-hydroxy-6-fluorophenanthridine, 85 mg of 2-amino-5-diethylaminotoluenehydrochloride (21) and 4 ml of ethanol at 20° C., a solution comprising258 mg of silver nitrate dissolved in 0.8 ml of water was added theretodrop-by-drop. Next, with 0.84 ml of 25% ammonia solution added, reactionwas allowed to proceed at 20° C. for a period of 24 hr. After thecompletion of the reaction, the reacted solution was introduced intowater. After extraction by chloroform, the extract was concentrated.After purification by column chromatography, 29 mg of indoanilinedescribed in the exemplified compound 3-131 was obtained as deep bluecrystal on recrystallization from hexane-ethyl acetate solvent (yield27.1%).

Analytical data

m.p.=177.8°-179.9 (°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 9.96(dd, 1H, J=13.0, 2.4 Hz), 9.40(s,1H),8.09(dd, 1H, J=8.9, 6.0 Hz), 7.59(d, 1H, J=10.4 Hz), 7.53(ddd, 1H,J=9.3, 8.9, 2.4 Hz), 6.85(d, 1H, J=10.4 Hz), 6.71(d, 1H, J=2.5 Hz),6.69(d, 1H, J=8.8 Hz) 6.56(dd, 1H, J=8.8, 2.5 Hz), 3.45(quartet, 4H,J=7.1 Hz), 2.52(s, 3H), 1,25(t, 6H, J=7.1 Hz)

¹³ C-NMR (ppm, ref.-TMS, d₆ -DMSO) 184.9, 164.9(d, J=242.0 Hz), 154.5,153.1, 148.1, 143.0, 137.9, 136.6, 134.8, 131.9, 131.2, 131.1, 130.2,127.5, 123.5, 119.2(d, J=25.8 Hz), 114.3(d, J=26.4 Hz), 113.8, 109.0,44.7, 20.0, 12.8

IR (cm⁻¹, KBr) 3435,2966, 2925, 1640, 1592, 1501, 1475, 1393, 1353,1262, 1232, 1196, 1147, 1113, 1079, 998, 997, 845, 799

MS (FAB, NBA)

m/z=388 (M⁺ +1)

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 647 nm (molar extinctioncoefficient=15,000).

1-11-5! Preparation of the indoaniline metal complex described in theexemplified compound 1-131

With 1.3 ml of aqueous solution containing 60.2 mg of copper perchloratehexahydrate (23) added to 2.5 ml of ethanol solution containing 25.0 mgof the indoaniline described in the exemplified compound 3-131, reactionwas allowed to proceed at 20° C. for a period of 20 hr. After thecompletion of the reaction, the precipitated crystals were taken out byfiltration and washed with a small amount of water and ethanol, followedby 4-hr reduced-pressure drying to obtain 30.0 mg of indoaniline metalcomplex described in the exemplified compound 1-131 as green crystals(yield 89.6%).

Analytical data

m.p.=300(°C.) or higher.

IR (cm⁻¹, KBr) 1622, 1590, 1576, 1533, 1449, 1417, 1381, 1327, 1276,1246, 1147, 1120, 1071, 1014, 985, 856, 822, 801, 739, 669, 630, 508,466

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 790 nm (molar extinctioncoefficient=129,000).

Example 2

Preparation of indoaniline metal complexes with the acridine skeleton

Prepared Example 2-1

Preparation of the indoaniline metal complex described in theexemplified compound 2-1

Synthesis was carried out in accordance with the following reactionscheme. ##STR18## 2-1-1! Synthesis of2-methoxydiphenylamine-2'-carboxylic acid (16)

A mixed solution comprising 7.84 g of o-anisidine (14), 4.99 g ofo-chlorobenzoic acid (15) and 500 mg of Copper (II) oxide was allowed toreact at 140° C. for a period of 3 hr. After the completion of thereaction, inorganic substances were removed from the reacted solution.After purifying the residue by column chromatography, 6.30 g of2-methoxydiphenylamine-2'-carboxylic acid (16) was obtained as crystalson recrystallization (yield 81.2%).

Analytical data

m.p.=174.0°-175.0 (°C.)

¹ H-NMR (ppm, ref.-TMS, d₆ -DMSO) 8.28(s, 1H), 6.58(dd, 1H, J=8.0, 1.3Hz), 6.06(d, 1H, J=7.6 Hz), 6.04 (td, 1H, J=7.7, 1.6 Hz) 5.87(d, 1H,J=8.2 Hz), 5.76-5.68 (m, 2H), 5.60(td, 1H, J=7.2, 2.0 Hz), 5.43(t, 1H,J=7.3 Hz), 3.38(s, 3H)

13C-NMR (ppm, ref.-TMS, d₆ -DMSO) 169.8, 150.9, 146.7, 134.0, 131.8,129.3, 123.4, 120.5, 120.2, 117.1, 113.6, 112.8, 111.8, 55.6

IR (cm⁻¹, KBr) 3374, 2946, 1667, 1593, 1573, 1519, 1491, 1469, 1450,1432, 1404, 1331, 1257, 1212, 1161, 1117, 1026, 909, 743, 671, 647, 569,486

MS (FAB, NBA)

m/z=242 (M⁺ +1)

2-1-2! Synthesis of 9-chloro-4-methoxyacridine (17)

A mixed solution comprising 3.06 g of2-methoxydiphenylamine-2'-carboxylic acid (16) and 15 g of phosphorylchloride was allowed to react at 100° C. for a period of 2 hr. After thecompletion of the reaction, the reacted solution was introduced into amixed solution comprising 10 ml of 25% ammonia solution, 25 g of ice and10 ml of chloroform. The reaction product was extracted by chloroform.After distilling chloroform away, the residue was purified by columnchromatography and 2.58 g of 9-chloro-4-methoxyacridine (17) wasobtained as crystals on recrystallization by hexane-chloroform (yield84.1%).

Analytical data

m.p.=125.0°-125.5 (°C.)

¹ H-NMR (ppm, ref.-TMS, d₆ -DMSO) 8.37(d,1H, J=8.6H), 7.90(d, 1H, J=8.8Hz), 7.86(d,1H, J=8.7 Hz), 7.65(br, 2H), 7.61(t, 1H, J=7.8 Hz), 7.30(t,1H, J=7.4 Hz), 7.19 (t, 1H, J=8.1 Hz), 6.99(d, 1H, J=7.4 Hz), 3.92(s,3H)

¹³ C-NMR (ppm, ref.-TMS, d₆ -DMSO) 154.9, 149.6, 147.6, 141.6, 129.5,129.2, 123.1, 121.9, 121.3, 114.6, 113.6, 113.2, 107.1, 55.3

IR (cm⁻¹, KBr) 3436, 1624, 1611, 1521, 1465, 1397, 1347, 1322, 1276,1263, 1225, 1157, 1095, 1077, 990, 872, 804, 794, 755, 733, 597

MS (FAB, NBA)

m/z=225 (M⁺ +1)

2-1-3! Synthesis of N₁ -9-(4-methoxy)acridinyl-N ₂-p-toluenesulfonylhydrazine hydrochloride (18)

A mixed solution comprising 817 mg of 9-chloro-4-methoxyacridine (17),749 mg of p-toluenesulfonylhydrazide and 20 ml of n-amyl alcohol wasallowed to react at 70° C. for a period of one hour. After thecompletion of the reaction, the reacted solution was cooled to roomtemperatures. Then, the precipitated crystals were collected byfiltering and washed with ethyl acetate. Thereafter, 1.33 g of N₁-9-acridinyl-N₂ -p-toluenesulfonylhydrazine hydrochloride (18) wasobtained as crystals on drying (yield 92.4%). Without purification atthis stage, the operation proceeded to the next reaction as it was.

2-1-4! Synthesis of 4-methoxyacridine (19)

A mixed solution comprising 124 mg of N₁ -9-(4-methoxy)acridinyl-N₂-p-toluenesulfonylhydrazine hydrochloride (18), 40 mg of sodiumhydroxide, and 5 ml of ethylene glycol was allowed to react at 100° C.for a period of one hour. After the completion of the reaction, thereacted solution was introduced into water and the product was extractedby ethyl acetate. After ethyl acetate was distilled away, the residuewas purified by column chromatography and 57.6 mg of 4-methoxyacridine(19) was obtained as crystals on recrystallization by hexane-ethylacetate (yield 95.2%).

Analytical data

m.p=127.0°-128.3 (°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 8.70(s, 1H), 8.40(d, 1H, J=8.9 Hz),7.95(d, 1H, J=8.4 Hz), 7.75(t, 1H, J=7.7 Hz), 7.55(d, 1H, J=8.4 Hz),7.52(t, 1H, J=7.5 Hz), 7.42(t, 1H, J=8.0 Hz), 7.02(d, 1H, J=7.4 Hz),4.15(s, 3H)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 155.1, 148.1, 142.0, 135.8, 130.2,129.9, 127.8, 127.5, 126.8 126.0, 125.6, 120.0, 106.5, 56.1

IR (cm⁻¹, KBr) 3444, 3003, 2953, 2827, 1624, 1560, 1530, 1465, 1402,1366, 1320, 1268, 1224, 1178, 1143, 1126, 1095, 964, 937, 854, 770, 737,718, 612, 572

MS (FAB, NBA)

m/z=210 (M⁺ +1)

2-1-5! Preparation of 4-hydroxyacridine (20)

A mixed solution comprising 510 mg of 4-methoxyacridine (19) and 10 mlof 48% hydrobromic acid was allowed to react at 110° C. for a period of14 hr. After the completion of the reaction, the reacted solution wasintroduced into an aqueous sodium carbonate solution water and theproduct was extracted by ethyl acetate. After ethyl acetate wasdistilled away, the residue was purified by column chromatography and420 mg of 4-hydroxyacridine (20) was obtained as crystals onrecrystallization by hexane-ethyl acetate (yield 88.3%).

Analytical data m.p=115.0°-115.5 (°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 8.59(s, 1H), 8.08(d, 1H, J=8.8 Hz),7.87(d, 1H, J=8.6 Hz), 7.65(t, 1H, J=7.7 Hz), 7.42(t, 1H, J=7.5 Hz),7.37-7.30(m, 2H), 7.09(d, 1H, J=7.7 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 151.7, 146.9, 140.2, 135.9, 130.2,129.0, 128.2, 127.2, 126.8 126.6, 125.9, 118.1, 108.4

IR (cm⁻¹, KBr) 3357, 3054, 2925, 2854, 1636, 1562, 1521, 1467, 1440,1399, 1369, 1321, 1228, 1212, 1129, 1070, 1035, 956, 919, 855, 771, 763,733, 722, 647, 612, 592, 560, 535, 474

MS (FAB, NBA)

m/z=196 (M⁺ +1)

2-1-6! Synthesis of the indoaniline (25) described in the exemplifiedcompound 4-1

While stirring a mixture comprising 195 mg of 4-hydroxyacridine (20),214 mg of 2-amino-5-diethylaminotoluene hydrochloride (21) and 6.8 ml ofethanol at 20° C., a solution comprising 0.17 mg of silver nitratedissolved in 0.75 ml of water was added thereto drop-by-drop. Next, with0.85 ml of 25% ammonia solution added to the mixture, reaction wasallowed to proceed at 20° C. for a period of 24 hr. After the completionof the reaction, the reacted solution was introduced into water. Afterextraction by ethyl acetate, the extract was concentrated. Afterpurification by column chromatography, 72.5 mg of indoaniline derivative(25) described in the exemplified compound 4-1 was obtained as deep bluecrystals on recrystallization by hexane-ethyl acetate (yield 19.6%).

Analytical data

m.p.=148.7 (°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 9.40(s, 1H), 8.45(d, 1H, J=8.7 Hz),8.05(d, 1H, J=8.2 Hz), 7.84(ddd, 1H, J=8.4, 7.5, 1.1 Hz), 7.68(t, 1H,J=7.2 Hz), 7.66(d, 1H, J=10.3 Hz), 6.96(d, 1H, J=10.3 Hz), 6.73-6.68(m,2H), 6.55(dd, 1H, J=8.8, 2.7 Hz), 3.43(q, 4H, J=7.1 Hz), 2.43(s, 3H),1.23(t, 6H, J=7.1 Hz)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 184.7, 149.2, 148.8, 147.6, 146.2,137.3, 135.9, 134.2, 133.0, 131.8, 131.3, 131.2, 129.5, 129.1, 128.8,128.7, 122.8, 113.8, 109.1, 44.6, 19.2, 12.8

IR (cm⁻¹, KBr) 2967, 1666, 1587, 1498, 1394, 1373, 1262, 1080

MS (FAB, NBA)

m/z=370 (M⁺ +1)

FIGS. 8, 9 and 10 show the spectral charts of ¹ H-NMR, ¹³ C-NMR and IR,respectively. The visible to near-infrared absorption spectrum (acetonesolution) had a maximum wavelength of absorption 606 nm (molarextinction coefficient=10,500).

2-1-7! Preparation of the indoaniline metal complex (26) described inthe exemplified compound 2-1

With 1.5 ml of aqueous solution containing 75.6 mg of copper perchloratehexahydrate (23) added to 3 ml of ethanol solution containing 30.0 mg ofindoaniline (25) described in the exemplified compound 4-1, reaction wasallowed to proceed at 20° C. for a period of 2 hr. After the completionof the reaction, the precipitated crystals were filtered off and washedwith a small amount of water and ethanol, followed by 4-hrreduced-pressure drying to obtain 31.5 mg of indoaniline metal complexes(26) described in the exemplified compounds 2-1 as black crystals (yield77.4%).

Analytical data

m.p.=300 (°C.) or higher

IR (cm⁻¹, KBr) 1569, 1530, 1462, 1393, 1376, 1325, 1286, 1247, 1143,1115, 1091, 1072, 1033, 990, 859

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 822 nm (molar extinctioncoefficient=97,000).

Prepared Example 2-2

Preparation of the indoaniline metal complex described in theexemplified compound 2-10

2-2-1! Synthesis of the indoaniline derivative described in theexemplified compound 4-10

While stirring a mixture comprising 2.87 g of 4-hydroxyacridine (20),4.89g of N,N-di(2-ethylhexyl)-p-phenylenediamine and 100 ml of ethanolat 20° C., a solution comprising 7.48 g of silver nitrate dissolved in33.1 ml of water was added thereto drop-by-drop. Next, with 12.5 ml of25% ammonia solution added to the mixture, reaction was allowed toproceed at 20° C. for a period of 24 hr. After the completion of thereaction, the reacted solution was introduced into water. Afterextraction by ethyl acetate, the extract was concentrated. Afterpurification by column chromatography, 0.99 g of indoaniline describedin the exemplified compound 4-10 was obtained as deep blue crystals onrecrystallization by hexane-ethyl acetate (yield 12.9%).

Analytical data

m.p.=108.1°-108.9 (°C.)

¹ H-NMR (ppm, ref.-TMS, CDCl₃) 9.370(s, 1H), 8.44(d, 1H, J=8.6 Hz),8.03(d, 1H, J=8.2 Hz), 7.83(t, 1H, J=8.2 Hz), 7.74(d, 1H, J=10.6 Hz),7.66(t, 1H, J=7.6 Hz), 7.08(d, 2H, J=8.6 Hz), 6.97(d, 1H, J=10.6 Hz),6.76(d, 2H, J=8.6 Hz), 3.44-3.23(m, 4H), 1.95-1,80(m, 2H), 1.54-1.18(m,16H), 1.06-0.77(m, 12H)

¹³ C-NMR (ppm, ref.-TMS, CDCl₃) 184.5, 149.7, 148.8, 147.9, 146.2,138.0, 134.2, 133.0, 131.8, 131.2, 129.4, 129.0, 128.8, 128.7, 125.3,112,8, 56.5, 37.0, 30.6, 28.7, 24.0, 23.9, 23.2, 14.1, 10.7

IR (cm⁻¹, KBr) 2980, 2926, 2858, 1663, 1607, 1582, 1508, 1461, 1364,1335, 1284, 1227, 1178, 1156, 1141, 1081, 826, 804

MS (FAB, NBA)

m/z=524 (M⁺ +1)

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 599 nm (molar extinctioncoefficient=21,000). 2-2-2! Preparation of the indoaniline metal complexdescribed in the exemplified compound 2-10

With 1.1 ml of aqueous solution containing 53.0 mg of copper perchloratehexahydrate (23) added to 3 ml of ethanol solution containing 30.0 mg ofindoaniline described in the exemplified compound 4-10, reaction wasallowed to proceed at 20° C. for a period of 20 hr. After the completionof the reaction, the precipitated crystals were filtered off and washedwith a small amount of water and ethanol, followed by 4-hrreduced-pressure drying to obtain 33.8 mg of indoaniline metal complexesdescribed in the exemplified compounds 2-10 as black crystals (yield90.1%).

Analytical data

m.p.=147.5°-150.4 (°C.)

IR (cm⁻¹, KBr) 2971, 2927, 2859, 1602, 1572, 1512, 1468, 1395, 1380,1362, 1329, 1291, 1180, 1136, 1095, 1028, 831, 741

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 840 nm (molar extinctioncoefficient=71,800).

Prepared Example 2-3

Preparation of the indoaniline metal complex described in theexemplified compound 2-57

With 1.1 ml of aqueous solution containing 52.4 mg of nickel perchloratehexahydrate (23) added to 3 ml of ethanol solution containing 30.0 mg ofindoaniline described in the exemplified compound 4-10, reaction wasallowed to proceed at 20° C. for a period of 20 hr. After the completionof the reaction, the deposited crystals were filtered off and washedwith a small amount of water and ethanol, followed by 4-hrreduced-pressure drying to obtain 20.7 mg of indoaniline metal complexesdescribed in the exemplified compounds 2-57 as black crystals (yield55.3%).

Analytical data

m.p.=147.0°-149.6 (°C.)

IR (cm⁻¹, KBr) 2971, 2928, 2870, 1605, 1516, 1460, 1378, 1361, 1331,1289, 1178, 1140, 1121, 1108, 827, 749, 628

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 818 nm (molar extinctioncoefficient=29,500).

Prepared Example 2-4

Preparation of the indoaniline metal complex described in theexemplified compound 2-58

With 1.1 ml of aqueous solution containing 75.0 mg of iron perchloratehydrate added to 3 ml of ethanol solution containing 30.0 mg ofindoaniline described in the exemplified compound 4-10, reaction wasallowed to proceed at 20° C. for a period of 20 hr. After the completionof the reaction, the precipitated crystals were filtered off and washedwith a small amount of water and ethanol, followed by 4-hrreduced-pressure drying to obtain 17.5 mg of indoaniline metal complexesdescribed in the exemplified compounds 2-58 as black crystals (yield43.6%).

Analytical data

m.p.=300 (°C.) or higher

IR (cm⁻¹, KBr) 2971, 2927, 2859, 1605, 1516, 1460, 1378, 1361, 1330,1289, 1235, 1137, 1121, 1102, 823, 759, 622

The visible to near-infrared absorption spectrum (acetone solution) hada maximum wavelength of absorption 764 nm (molar extinctioncoefficient=16,600).

Example 3

Manufacturing method of transparent recording medium

Example 3-1

The following mixture was dissolved in an organic solvent (methyl ethylketone) to a solid content of 20%.

Developer: n-propyl gallate tri-N-phenylcarbamate 20 parts

Organic acid metal salt: iron o-benzoylbenzoate 20 parts

Binder: polyvinyl butyral 20 parts

Near-infrared absorbing material: indoaniline metal complex described inthe exemplified compound 1-1 1 part

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayer bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec using asemiconductor laser beam with a 30 mW output, black recorded images of a50 μm line width were obtained. On projecting this transparent recordingmedium mounted on a slide, the black images could be magnified clearlywith high resolution. Also, on projecting this transparent recordingmedium over an OHP, the black images could be magnified clearly withhigh resolution. A heat resistance test at 60° C. revealed absolutely nocolor change. Even if exposed to sunlight for a week, the transparentrecording medium exhibited no change in color.

Example 3-2

The following mixture was dissolved in an organic solvent (methyl ethylketone) to a solid content of 20%.

Developer: n-propyl gallate tri-N-phenylcarbamate 20 parts

Organic acid metal salt: iron o-benzoylbenzoate 20 parts

Binder: polyvinyl butyral 20 parts

Near-infrared absorbing material: indoaniline metal complex described inthe exemplified compound 2-1 1 part

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayer bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, black recorded images of a55 μm line width were obtained. On projecting this transparent recordingmedium mounted on a slide, the black images could be magnified clearlywith high resolution. Also, on projecting this transparent recordingmedium over an OHP, the black images could be magnified clearly withhigh resolution. A heat resistance test at 60° C. revealed absolutely nocolor change. Even if exposed to sunlight for a week, the transparentrecording medium exhibited no change in color.

Example 3-3

Except for substitution of 20 parts of an UV-curable resin GRANDICUV5020 (available from Dainippon Ink & Chemicals Inc.) for the binder inthe coating liquid for recording of Example 3-1, a coating liquid forrecording was obtained in exactly the same manner as with Example 3-1.After applying the resultant recording coating liquid in an amount of 5g/m² to a transparent polyester film by using a Mayer bar, a transparentrecording medium was obtained, with the film moved at a speed of 5m/min, by using the UV-curable resin with ultraviolet ray irradiatedfrom a UV emitter (one lamp, output 3 kW, available from the EyegraphicCo.) at a distance of 12 cm from the surface of the coated layer. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, black recorded images of a50 μm line width were obtained.

Example 3-4

Except for substitution of 20 parts of an UV-curable resin GRANDICUV5020 (available from Dainippon Ink & Chemicals Inc.) for the binder inthe coating liquid for recording of Example 3-2, a coating liquid forrecording was obtained in exactly the same manner as with Example 3-2.After applying the resultant recording coating liquid in an amount of 5g/m² to a transparent polyester film by using a Mayer bar, a transparentrecording medium was obtained, with the film moved at a speed of 5m/min, by using the UV-curable resin with ultraviolet ray irradiatedfrom a UV emitter (one lamp, output 3 kW, available from the EyegraphicCo.) at a distance of 12 cm from the surface of the coated layer. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, black recorded images of a55 μm line width were obtained.

Example 3-5

The following mixture was dissolved in an organic solvent (toluene) to asolid content of 20%.

Developer: n-propyl gallate tri-N-phenylcarbamate 5 parts

Organic acid metal salt: iron o-benzoylbenzoate 20 parts

Binder: polyvinyl butyral 20 parts

Near-infrared absorbing material: indoaniline metal complex described inthe exemplified compound 1-2 1 part

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayer bar in an amount of 5g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, black recorded images of a45 μm line width were obtained.

Example 3-6

The following mixture was dissolved in an organic solvent (toluene) to asolid content of 20%.

Developer: n-propyl gallate tri-N-phenylcarbamate 5 parts

Organic acid metal salt: iron o-benzoylbenzoate 20 parts

Binder: polyvinyl butyral 20 parts

Near-infrared absorbing material: indoaniline metal complex described inthe exemplified compound 1-7 1 part

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayer bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, black recorded images of a45 μm line width were obtained.

Example 3-7

The following mixture was dissolved in an organic solvent (methylisobutyl ketone) to a solid content of 25%.

Developer: n-propyl gallate tri-N-phenylcarbamate 5 parts

Organic acid metal salt: iron o-benzoylbenzoate 20 parts

Binder: polyvinyl butyral 20 parts

Near-infrared absorbing material A!: indoaniline metal complex describedin the exemplified compound 1-10 1 part

Near-infrared absorbing material B!: NK-2014 (Nippon Kankoh-ShikisoKenkyusho Co., Ltd.) 0.1 part

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayer bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, black recorded images of a45 μm line width were obtained.

Example 3-8

The following mixture was dissolved in an organic solvent (methylisobutyl ketone) to a solid content of 25%.

Developer: n-propyl gallate tri-N-phenylcarbamate 5 parts

Organic acid metal salt: iron o-benzoylbenzoate 20 parts

Binder: polyvinyl butyral 20 parts

Near-infrared absorbing material A!: indoaniline metal complex describedin the exemplified compound 1-11 1 part

Near-infrared absorbing material B!: NK- 1144 (Nippon Kankoh-ShikisoKenkyusho Co., Ltd.) 0.1 part

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayor bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, black recorded images of a45 μm line width were obtained.

Example 3-9

The following mixture was dissolved in an organic solvent (chloroform)to a solid content of 10%.

Developer: n-propyl gallate tri-N-cyclohexylcarbamate 8 parts

Organic acid metal salt: iron o-benzoylbenzoate 12 parts

Binder: polyvinyl butyral 20 parts

Near-infrared absorbing material A!: indoaniline metal complex describedin the exemplified compound 1-15 1 part

Near-infrared absorbing material B!: NIR-14 (Yamamoto Chemical Ind.) 0.1part

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayer bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, black recorded images of a50 μm line width were obtained.

Example 3-10

The following mixture was dissolved in an organic solvent (chloroform)to a solid content of 10%.

Developer: n-propyl gallate tri-N-cyclohexylcarbamate 8 parts

Organic acid metal salt: iron o-benzoylbenzoate 12 parts

Binder: polyvinyl butyral 20 parts

Near-infrared absorbing material A!: indoaniline metal complex describedin the exemplified compound 1-25 1 part

Near-infrared absorbing material B!: PA-1006 (Mitsui ToAtsu ChemicalsK.K.) 0.1 part

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayer bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, black recorded images of a55 μm line width were obtained.

Example 3-11

The following mixture was dissolved in an organic solvent(chloroform/acetone) to a solid content of 20%.

Developer: n-propyl gallate trimethylcarbonate 20 parts

Leuco dye: crystal violet lactone 20 parts

Binder: polystyrene 20 parts

Near-infrared absorbing material: indoaniline metal complex described inthe exemplified compound 1-53 3 parts

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayer bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec using asemiconductor laser beam with a 30 mW output, blue recorded images of a40 μm line width were obtained. On projecting this transparent recordingmedium mounted on a slide, the blue images could be magnified clearlywith high resolution. A heat resistance test at 60° C. revealedabsolutely no color change.

Example 3-12

The following mixture was dissolved in an organic solvent (chloroformacetone) to a solid content of 20%.

Developer: n-propyl gallate trimethylcarbonate 20 parts

Leuco dye: crystal violet lactone 20 parts

Binder: polystyrene 20 parts

Near-infrared absorbing material:indoaniline metal complex described inthe exemplified compound 1-57 3 parts

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayer bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, blue recorded images of a35 μm line width were obtained. On projecting this transparent recordingmedium mounted on a slide, the black images could be magnified clearlywith high resolution. A heat resistance test at 60° C. revealedabsolutely no color change.

Example 3-13

The following mixture was dissolved in an organic solvent (toluene) to asolid content of 20%.

Developer: n-propyl gallate tri-N-phenylcarbamate 5 parts

Organic acid metallic salt: iron o-benzoylbenzoate 20 parts

Binder: polystyrene 20 parts

Near-infrared absorbing material: indoaniline metal complex described inthe exemplified compound 1-58 1 part

Singlet oxygen quencher: salicylaldoxime 0.1 part

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayer bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, black recorded images of a45 μm line width were obtained.

Example 3-14

The following mixture was dissolved in an organic solvent (toluene) to asolid content of 20%.

Developer: n-propyl gallate tri-N-phenylcarbamate 5 parts

Organic acid metal salt: iron o-benzoylbenzoate 20 parts

Binder: polystyrene 20 parts

Near-infrared absorbing material: indoaniline metal complex described inthe exemplified compound 1-131 1 part

Singlet oxygen quencher: salicylaldoxime 0.1 part

The resultant coating liquid for recording was applied to a transparentpolyester film by using a Mayer bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec by using asemiconductor laser beam with a 30 mW output, black recorded images of a45 μm line width were obtained.

Example 3-15

The following mixture was dissolved in an organic solvent(toluene/methyl ethyl ketone) to a solid content of 20%.

Developer: n-propyl gallate tri-N-phenylcarbamate 5 parts

Organic acid metal salt: iron o-benzoylbenzoate 20 parts

Binder: polystyrene 20 parts

Near-infrared absorbing material: indoaniline metal complex described inthe exemplified compound 2-10 1 part

The resultant coating liquid for recording was applied to a transparentpolyester film using a Mayer bar in an amount of 5 g/m², and dried inair at room temperature to obtain a transparent recording medium. Whenthis transparent recording medium was scanned at 40 mm/sec using asemiconductor laser beam with a 30 mW output, black recorded lines of a55 μm line width were obtained.

Example 4

Example of printing, by use of a masking material according to thepresent invention

Example 4-1

On the transparent recording medium obtained in Example 3-1, blackimages and characters were recorded using near-infrared semiconductorlaser rays with an output power 30 mW. With the transparent recordingmedium on which images and characters were recorded and a PS-plate madeby Fuji Photo Film Co., Ltd. (VPS (positive)) mutually overlapped, raysof a metal halide lamp (wavelength: 417 nm) were irradiated to them fromthe side of the transparent recording medium and images were exposed.The printing plate for offset print obtained in this manner, was loadedon a printer (Hamada 611XL) for offset plate and printed ontofine-quality paper (woodfree paper) and coated paper. Images andcharacters of a printed substance had exactly the same image quality aswith those recorded on the transparent recording medium and neitherbackground stain in the non-image portion nor deteriorated images in theimage portion thereof were observed at all even for more than 5000printed sheets.

Example 4-2

On the transparent recording medium obtained in Example 3-2, blackimages and characters were recorded using near-infrared semiconductorlaser rays with an output power 30 mW. With the transparent recordingmedium on which images and characters were recorded and a PS-plate madeby Fuji Photo Film Co., Ltd. (VPS (positive)) mutually overlapped, raysof a metal halide lamp (wavelength: 417 nm) were irradiated to them fromthe side of the transparent recording medium and images were exposed.The printing plate for offset print obtained in this manner, was loadedon a printer (Hamada 611XL) for offset plate and printed ontofine-quality paper (woodfree paper) and coated paper. Images andcharacters of a printed substance had exactly the same image quality aswith those recorded on the transparent recording medium and neitherbackground stain in the non-image portion nor deteriorated images in theimage portion thereof were observed at all even for more than 5000printed sheets.

Example 4-3

On the transparent recording medium obtained in Example 3-15, blackimages and characters were recorded using near-infrared semiconductorlaser rays with an output power 30 mW. With the transparent recordingmedium on which images and characters were recorded and a PS-plate madeby Fuji Photo Film Co., Ltd. (VPS (positive)) mutually overlapped, raysof a metal halide lamp (wavelength: 417 nm) were irradiated to them fromthe side of the transparent recording medium and images were exposed.The printing plate for offset print obtained in this manner, was loadedon a printer (Hamada 611XL) for offset plate and printed ontofine-quality paper (woodfree paper) and coated paper. Images andcharacters of a printed substance had exactly the same image quality aswith those recorded on the transparent recording medium and neitherbackground stain in the non-image portion nor deteriorated images in theimage portion thereof were observed at all even for more than 5000printed sheets.

Example 5

Manufacturing method of an optical recording medium

Example 5-1

A homogeneous coating liquid composed of the following constituents wasadded thereto drop-by-drop onto a transparent polyester film, coatedover the whole film at a rotation rate of 500 rpm by the spinner methodand dried at 40° C. for a period of 20 min.

Near-infrared absorbing material: indoaniline metal complex described inthe exemplified compound 1- 1 1 part

Organic solvent: acetone 50 part

When this optical recording medium was irradiated with a near-infraredsemiconductor laser beam with a 5 mW output, a spot of 4.1 μm diameterwas obtained.

Example 5-2

A homogeneous coating liquid composed of the following constituents wasadded thereto drop-by-drop onto a transparent polyester film, coatedover the whole film at a rotation rate of 500 rpm by the spinner methodand dried at 40° C. for a period of 20 min.

Near-infrared absorbing material: indoaniline metal complex described inthe exemplified compound 3-1 1 part

Organic solvent: acetone 50 part

When this optical recording medium was irradiated with a near-infraredsemiconductor laser beam with a 5 mW output, a spot of 4.3 m diameterwas obtained.

Example 5-3

Near-infrared absorbing material: indoaniline metal complex described inthe exemplified compound 2-10 1 part

Organic solvent: acetone 50 parts

A homogeneous coating liquid composed of the following constituents wasadded thereto drop-by-drop onto a transparent polyester film, coatedover the whole film at a rotation rate of 500 rpm by the spinner methodand dried at 40° C. for a period of 20 min. When this optical recordingmedium was irradiated with a near-infrared semiconductor laser beam witha 5 mW output power, a spot of 4.5 μm diameter was obtained.

Comparative Examples Comparative example 1-1

Except that one part of indoaniline metal complex represented by thefollowing structural formula (27) was employed in place of thenear-infrared absorbing material of Example 3-1, a transparent recordingmedium was manufactured in exactly the same manner as with Example 3-1.##STR19##

When this transparent recording medium was scanned at 40 mm/sec using asemiconductor laser beam with a 30 mW output, black recorded images of a40 μm line width were obtained.

However, the coloration of the obtained transparent recording medium wasso deep that images lacking in contrast were obtained.

Comparative example 1-2

Except that one part of NK-2014 (Nippon Kankoh-Shikiso Kenkyusho Co.,Ltd.) was employed in place of the near-infrared absorbing material ofExample 3-1, a transparent recording medium was manufactured in exactlythe same manner as with Example 3-1.

When this transparent recording medium was scanned at 40 mm/sec by usinga semiconductor laser beam with a 30 mW output, black recorded images ofa 40 μm line width were obtained. However, when exposed to sunlight forthree days, the transparent recording medium changed color from lightyellow green to brown.

Comparative example 1-3

Except that one part of benzoin nickel complex was employed in place ofthe near-infrared absorbing material of Example 3-1, a transparentrecording medium was manufactured in exactly the same manner as withExample 3-1. However, a transparent recording medium having an unevencoated surface and lacking in transparency was obtained.

Comparative example 2-1

Except that the transparent recording medium of Comparative Example 1-1was employed in place of the transparent recording medium of Example3-1, a plate for offset print was obtained. Images and characters in aprint substance obtained by printing with this plate were unclear.

Comparative example 3-1

Except that one part of indoaniline metal complex represented by theabove structural formula (27) was employed in place of the near-infraredabsorbing material of Example 5-1, an optical recording medium wasmanufactured in exactly the same manner as with Example 5-1. When thisoptical recording medium was irradiated with a near-infraredsemiconductor laser beam with a 5 mW output, however, only a spot of 2.1μm diameter was obtained.

A new indoaniline metal complex according to the present invention has alarge absorption in the near-infrared range, exhibiting a high molarextinction coefficient and a greatly improved efficiency of convertingnear-infrared laser rays into heat as compared with a conventionalindoaniline metal complex. Because of decreasing in visible absorptionand exhibiting a high recording density in record by near-infrared laserrays, a transparent recording medium, made up using this new indoanilinemetal complex as a near-infrared absorbing material, is quite excellentin the contrast of images. In addition, because of exhibiting no changewhatever in color, molar extinction coefficient and the efficiency ofconverting near-infrared laser rays into heat, a new indoaniline metalcomplex according to the present invention is a coloring substance quiteexcellent in light resistance and consequently a transparent recordingmedium made up using this metal complex is also excellent in lightresistance. Furthermore, according to the present invention, newindoaniline metal complexes and new indoaniline derivatives according tothe present invention are applicable to green-type coloring substances,heat-sensitive coloring substances, ink jet printer coloring substances,optical disks, heat-ray intercepting agents, safe light filters forphotosensitive materials, cut filters of semiconductor elements, colorfilters, liquid crystals, anti-halation materials for photosensitivematerials, optical cards, photopolymerization initiators,physiologically active matters, medicaments and the like.

We claim:
 1. An acridine derivative of formula 4: ##STR20## wherein R¹and R² each independently are a hydrogen atom, alkyl group, or arylgroup, or jointly form a five- or six-member nitrogen heterocycle or apolycyclic ring containing said five- or six-member nitrogenheterocycle; R³ is a hydrogen atom or electron donating groups; and R⁴,R⁷, and R⁸ each independently are a hydrogen atom or electronwithdrawing groups; whereas l and o are each independently an integer of1-4; and m is an integer of 1 or
 2. 2. An acridine derivative accordingto claim 1, wherein R¹ and R² are each selected from the groupconsisting of a hydrogen atom, alkyl group, and aryl group, or R¹ and R²jointly form a five- or six-member nitrogen heterocycle; R³ is selectedfrom the group consisting of a hydrogen atom, alkyl group, aralkylgroup, alkoxy group, aryloxy group, alkylthio group, arylthio group, andalkyl-substituted amino group; R⁴, R⁷, and R⁸ are each selected from thegroup consisting of a hydrogen atom, halogen atom, trifluoromethyl,cyano, aryl group, carbonyl, hydroxycarbonyl, alkoxycarbonyl,aryloxycarbonyl, aminothiocarbonyl, carbamoyl, sulfonyl and sulfamoyl; land o are each 1, 2, or 3; and m is
 1. 3. An acridine derivativeaccording to claim 2, wherein R¹ and R² are each selected from the groupconsisting of a hydrogen atom, methyl, ethyl, propyl, butyl, pentyl,hexyl, 2-ethylhexyl, cetyl, 2-ethoxyethyl, methoxyethoxyl, benzyl,2-carboxyethyl, 2-cyanoethyl, 2-chloroethyl, 2-benzyloxyethyl,methylcarbonyloxyethyl, 2-phenoxyethyl, 2-acetoxyethyl,ethoxycarbonylmethyl, 3-mesylpropyl, 2-propenyl, 2-oxolanylmethyl,propenyl, p-tolyl, p-chlorophenyl, p-methoxyphenyl, p-n-butoxyphenyl,2-methyl-2-propenyl, 2-chloro-2-propenyl, and cyclohexyl; or R¹ and R²jointly form a piperidinyl or morpholinyl.
 4. An acridine derivativeaccording to claim 2, wherein R³ is selected from the group consistingof a hydrogen atom, methyl, ethyl, cyclohexyl, 2-methoxyethyl,2-allyloxyethyl, benzyl, methoxy, ethoxy, phenoxy, diethylamino,diisopropylamino, tosylamino, mesylamino, lauloylamino, palmitoylamino,stearoylamino, 1-naphthoylamino, methylthio, n-butylthio, phenylthio,p-chlorophenylthio, benzylthio, N-n-propylureido, N,N-diethylureido,thioureido, and N-acetyl-N-phenylthioreido.
 5. An acridine derivativeaccording to claim 2, wherein R⁴ is selected from the group consistingof a hydrogen atom, acetyl, isovaleryl, stearoyl, benzoyl, 1-naphthoyl,carboxy, phenylcarbamoyl, methylcarbamoyl, ethoxymethylcarbamoyl,2-oxolanylmethylcarbamouyl, allylcarbamoyl,3-(2-methoxycarbonyl)thienylcarbamoyl, 2-thiazolylcarbamoyl,2-benzoimidazolylcarbamoyl, 2-benzoxazolylcarbamolyl,2-benzothioazolylcarbamoyl, 2-pyridylcarbamoyl, 4-pyrimidylcarbamoyl,2-qunolylcarbamoyl, 3H-indo-2-lylcarbamoyl, sulfo, phenylsufamoyl,methylsulfamoyl, ethoxymethylsufamoyl, 2-oxolanylmethylsulfamoyl,allylsufamoyl, 2-thienylsufamoyl, 2-thiazolylsulfamnoyl,2-benzoimidazolylsufamoyl, 2-benzoxazolylsulfamoyl,2-benzothiazolylsulfamoyl, 2-pyridylsulfamoyl, 4-pyrimidylsulfamoyl,2-quinolysulfamoyl, 3H-indo-2-lylsulfamoyl, methoxycarbonyl,ethylcarboxyl, n-butoxycarbonyl, lauryloxycarbaonyl, stearyloxycarbonyl,phenoxycarbonyl, p-tolyloxycarbonyl, p-chlorophenoxycarbonyl,p-methoxyphenocarbonyl, nitro, cyano, chloro, bromo, and fluoro.
 6. Anacridine derivative according to claim 2, wherein R⁷ is selected fromthe group consisting of a hydrogen atom, phenyl, fluoro, chloro, bromo,iodo, trifluoromethyl, cyano, o-tolyl, o-hydroxyphenyl, chlorophenyl,bromophenyl, iodophenyl, 3-pyridinyl, benzensulfonyl, p-tolenesulfonyl,formyl, acetyl, hydroxyiminomethylcarbonyl, bromoacetyl,hydroxycarbonyl, methoxycarbonyl, n-hexylcarbonyl, aminothiocarbonyl,and hydroxycarbonylmethyl.
 7. An acridine derivative according to claim2, wherein R⁸ is selected from the group consisting of a hydrogen atom,fluoro, chloro, phenyl, tolyl, chlorophenyl, methoxyphenyl,butoxyphenyl, methoxycarbonyl, ethoxycarbonyl, cyano, trifluoromethyl,nitro, carboxyl, phenoxycarbonyl, tolyloxycarbonyl,bromophenoxycarbonyl, acetyl, propionyl, isovaleryl, stearoyl, benzoyl,phenylcarbamoyl, methylcarbamoyl, allylcarbamoyl, thienylcarbamoyl,benzothiazolylcarbamoyl, 2-pyridylcarbamoyl 3H-indo-2-lylcarbamoyl,phenysulfamoyl, methylsulfamoyl, 2-oxolanylmethylsulfamoyl,2-thiazolylsulfamoyl, benzoimidazolylsufamoyl, and pyrimidylsulfamoyl.8. An acridine derivative according to claim 1, wherein R¹ and R² areeach ethyl or 2-ethylhexyl; R³ is a hydrogen atom, methyl or methoxy;R⁴, R⁷, and R⁸ are each a hydrogen atom or halogen atom; l, m, and o areeach
 1. 9. An acridine derivative according to claim 3, wherein R¹ andR² are each ethyl or 2-ethylhexyl.
 10. An acridine derivative accordingto claim 4, wherein R³ is a hydrogen atom, methyl, or methoxy; R⁴, R⁷,and R⁸ are each a hydrogen atom or halogen atom.
 11. An acridinederivative according to claim 2, wherein l, m and o are each 1.